JP5724248B2 - Colored resin composition for color filter, color filter, liquid crystal display device and organic EL display - Google Patents

Description

  The present invention relates to a colored resin composition capable of providing a pixel for a color filter excellent in spectral characteristics and heat resistance, a color filter having a pixel formed using the same, and a liquid crystal display formed using the color filter The present invention relates to an apparatus and an organic EL display.

In recent years, color liquid crystal display devices and organic EL displays have attracted attention as flat displays, and color filters are used for these displays.
For example, a color liquid crystal display device includes, as an example, a black matrix, a colored layer composed of a plurality of colors (usually three primary colors of red (R), green (G), and blue (B)), a transparent electrode, and an alignment layer. The color filter substrate provided, the thin film transistor (TFT element), the counter electrode substrate provided with the pixel electrode and the alignment layer, and the two substrates are opposed to each other with a predetermined gap, sealed with a sealing member, There is a transmissive liquid crystal display device that is roughly configured from a liquid crystal layer formed by injecting a liquid crystal material. There is also a reflective liquid crystal display device in which a reflective layer is provided between the color filter substrate and the colored layer.

  On the other hand, in principle, an organic EL display has an organic EL element having a structure in which an organic EL light-emitting layer is sandwiched between an anode and a cathode. In order to obtain a possible organic EL display, (1) a method of arranging organic EL elements that emit light of each of the three primary colors, (2) a method of combining organic EL elements that emit white light with a color filter layer of the three primary colors, And (3) a CCM system that combines an organic EL element that emits blue light and a color conversion layer (CCM layer) that performs color conversion from blue to green and blue to red, respectively.

Needless to say, the method of (1) is characterized in that high color reproducibility can be exhibited because organic EL elements of each color are used. Therefore, by placing color filters corresponding to the organic EL elements of each color, improvement in color reproducibility and improvement in contrast by absorbing reflected light can be expected. .
In addition, the combination method of the white organic EL and the color filter in (2) and the CCM method in (3) may use only one type of organic EL element that emits light of the same color. Unlike the EL display, it is not necessary to align the characteristics of the organic EL elements of each color, and the number of processes and materials can be reduced.

  In an organic EL element using a color filter and a color conversion method including a color conversion filter and an organic light emitter, heat resistance required in the color display manufacturing process, weather resistance when used as a display, and For those that require high-definition images, color filters created by the pigment dispersion method are the mainstream, and red, blue, or green pigments in the photosensitive resin solution have a particle size of 1 μm or less. After the finely dispersed material is applied on a glass substrate, pixels are formed in a desired pattern by photolithography.

With respect to color filters, improvements in color purity, saturation, and light transmission are required. Conventionally, for the purpose of improving light transmission, the content of the color pigment relative to the photosensitive resin in the image forming material is reduced. A method of reducing the thickness of a pixel formed by an image forming material has been employed. However, in these methods, the saturation of the color filter itself is lowered, the entire display becomes whitish, and the vividness of the color necessary for display is sacrificed. When it is increased, the entire display becomes dark, and in this case, the amount of light of the backlight must be increased in order to ensure brightness, leading to an increase in power consumption of the display.

On the other hand, for the purpose of improving the light transmission amount, a method of finely dispersing the pigment particle diameter to 1/2 or less of the coloration wavelength is known (Non-Patent Document 1). Since the coloration wavelength is shorter than that of other red and green pigments, further fine dispersion is required in this case, resulting in problems of cost increase and stability after dispersion.
On the other hand, color filters using dyes as colorants are still being developed. For example, Patent Document 1 describes a color filter provided with a blue filter layer containing C.I. Acid Blue 83 (triallylamine dye) and C.I. Solvent Blue 67 (copper phthalocyanine dye). ing.

However, the color filter using the dye described in the document has a problem that spectral characteristics, heat resistance, and light resistance are insufficient.
Patent Document 2 describes a color filter using a polymer containing a polymerizable triphenylmethane dye represented by the following general formula.
However, although the color filter using the dye described in the document has excellent spectral characteristics, it has a problem of insufficient light resistance and heat resistance.

Furthermore, Patent Document 3 also describes a color resin composition for a color filter containing a compound (pigment) represented by a specific structure.
However, the present inventors have found that these compounds (dyes) are not sufficient in terms of heat resistance.

Japanese Patent Laid-Open No. 2002-14222 JP 2000-162429 A JP 2008-304766 A

Kiyoshi Hashizume “Journal of Color Material Association” (December 1967, page 608)

An object of the present invention is to provide a color resin composition that can provide a pixel for a color filter excellent in light resistance and also satisfies the heat resistance required in the color display manufacturing process described above. Another object of the present invention is to provide a color filter excellent in color purity and transmittance of a pixel by using such a colored resin composition, a liquid crystal display device and an organic EL display with good color purity using the color filter. And

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a compound (pigment) having a specific structure as a color material for forming a color filter pixel. It was completed.
That is, the gist of the present invention resides in the following (1) to (12).
(1) A color filter comprising (a) a color material, (b) a solvent, and (c) a binder resin, wherein (a) the color material contains a compound represented by the following general formula (I) Coloring resin composition.

(In the above general formula (I), [Z] ^m- represents an arbitrary m-valent anion.
R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. When R ^{1 to} R ⁶ represent an alkyl group which may have a substituent, adjacent R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ are bonded to form a ring structure. It may be.

X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.
Y each independently represents a hydrogen atom or an arbitrary substituent.
In addition, multiple molecules in one molecule

May be the same structure or different structures.
m represents an arbitrary natural number. )
(2) The colored resin composition for color filters as described in (1) above, wherein the compound represented by the general formula (I) is a compound represented by the general formula (i).

(R ^{1 to} R ⁶ , X, Y, [Z] ^m− and m in the general formula (i) are all the same as those in the general formula (I).)
(3) The colored resin composition for a color filter according to (1) or (2), wherein X is a methyl group.
(4) The colored resin composition for a color filter according to any one of (1) to (3), wherein at least one of the R ^{1 to} R ⁶ is a fluorine atom-containing group.

(5) The colored resin composition for a color filter according to any one of (1) to (4), wherein the [Z] ^m− is a sulfonate anion.
(6) The color filter coloring as described in any one of (1) to (5) above, wherein the compound represented by the general formula (I) is a compound represented by the general formula (v) Resin composition.

(In the general formula (v), m, Y, and R ^{1 to} R ⁵ have the same meanings as in the general formula (I).
Moreover, it is particularly preferable that at least one of R ^{1 to} R ⁵ is a fluorine atom-containing group or a branched alkyl group. More specifically, for example, a fluoroalkyl group or an isobutyl group can be mentioned.

R ³¹ represents a hydrogen atom or a phenyl group which may have a substituent,
R ^{32 to} R ³⁴ each independently represent a hydrogen atom, a hydroxyl group, —NHR ⁴¹ (R ⁴¹ has the same meaning as R ³¹ ), —SO ₃ ^— , a halogen atom, —CO ₂ R ⁴² (R ⁴² represents carbon. Represents an alkyl group represented by formulas 1 to 3, and at least one of R ^{32 to} R ³⁴ is a —NHR ⁴¹ group.

R ^{35 to} R ³⁸ are each independently a hydrogen atom, —SO ₃ ^— , a halogen atom, a phenoxy group, a naphthyloxy group, an alkoxyl group having 1 to 12 carbon atoms, —CO ₂ R ⁴³ , a phenyl group, —SO _3. R ⁴⁴ or —SO ₂ NHR ⁴⁵ (wherein R ^{43 to} R ⁴⁵ each independently represents an alkyl group having 1 to 6 carbon atoms).
Further, m —SO ₃ ^— groups are bonded in one anthraquinone skeleton.

In addition, when two or more cation frame | skeleton specified in the said general formula (v) is contained in 1 molecule, they may be the same structure or a different structure. )
(7) The content of the compound represented by the general formula (I) is 5% by weight or more based on the total amount of the color material (a), and any one of (1) to (6) The colored resin composition for color filters according to item 1.

(8) The colored resin composition for a color filter according to any one of (1) to (7), further comprising (f) a polymerizable monomer.
(9) The colored resin for a color filter according to any one of (1) to (8), further comprising (g) a photopolymerization initiator and / or a thermal polymerization initiator. Composition.
(10) A color filter having a pixel produced using the colored resin composition for a color filter according to any one of (1) to (9).

(11) A liquid crystal display device comprising the color filter according to (10).
(12) An organic EL display comprising the color filter according to (10).

According to the present invention, the color filter satisfies the light resistance which is an extremely important item among the long-term reliability of the color filter, has the heat resistance required in the color display manufacturing process, and has excellent color purity and transmittance of the pixel. A color filter can be obtained.
By using such a color filter, the light emission of the organic EL display and the light emission of the backlight of the color filter can be taken out efficiently, and a liquid crystal display device and an organic EL display that achieve both high color reproducibility and high luminance. Can be provided.

  In particular, the contrast of the liquid crystal display device can be improved.

The constituent requirements and embodiments of the present invention will be described in detail below, but these are examples of the embodiments of the present invention, and the present invention is not limited to these contents.
“(Meth) acryl” and the like mean “at least one of acryl and methacryl” and “(meth) acrylate” and the like mean “at least one of acrylate and methacrylate”. “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

Further, “total solid content” means all components other than the solvent components described later, which are contained in the pigment dispersion or the colored resin composition.
In the present invention, unless otherwise specified, the weight average molecular weight refers to a polystyrene-reduced weight average molecular weight (Mw) by GPC (gel permeation chromatography). “C.I.” means a color index (C.I.).

  Furthermore, in the present invention, the “amine value” means an amine value in terms of effective solid content unless otherwise specified, and is a value represented by the amount of base and the equivalent weight of KOH per 1 g of the solid content of the dispersant. is there. The measuring method will be described later. On the other hand, the “acid value” represents an acid value in terms of effective solid content unless otherwise specified, and is calculated by neutralization titration.

It is a chart which shows the transmission spectrum of the UV cut filter used in the case of the light resistance test in an Example. It is a chart which shows the transmission spectrum of the polarizing plate used in the case of the light resistance test in an Example. It is a cross-sectional schematic diagram which shows an example of the organic EL element provided with the blue color filter of this invention. It is typical sectional drawing which shows the structure of the organic electroluminescent light emitting element created in the Example.

<Constituent components of colored resin composition>
Below, each component of the colored resin composition of this invention is demonstrated.
The colored resin composition of the present invention comprises (a) a color material having a specific structure, (b) a solvent, and (c) a binder resin as essential components, and if necessary, other additives other than the above components, and Other colorants such as pigments may be blended.

Hereinafter, each component will be described.
<(A) Color material>
The colored resin composition for a color filter of the present invention comprises (a) a color material, (b) a solvent, and (c) a binder resin, wherein (a) the color material is a compound represented by the following general formula (I). It is characterized by containing.

The reason why it is excellent in heat resistance and contrast by using the compound represented by the following general formula (I) contained in the color material (a) of the present invention is estimated as follows.
In order to ensure the color characteristics of the compound having a triarylmethane structure, the three aryl groups substituted on the central carbon atom having a positive charge need to be moderately twisted.
Further, the central carbon atom having a positive charge has high reactivity and is likely to react with a compound present in the periphery.
That is, in order to improve the heat resistance of a compound having a triarylmethane structure, it is conceivable to first cause twisting to such an extent that the color characteristics are not affected, thereby increasing the steric hindrance around the central carbon atom.
In the compound represented by the general formula (I) of the present invention, two benzene rings, one naphthalene ring, and three aromatic rings in the molecule are bonded through one carbon atom.
For this reason, the twist becomes larger than that in the case where there are three benzene rings, so that a positive charge existing in the central carbon atom in the formula (I) has a highly reactive compound (for example, oxygen molecule or Polymerizable reaction initiators) are difficult to attack.
Here, in Formula (I), it has a halogen group or a C1-C8 alkyl group as X group. These groups have no effect on twist, but increase steric hindrance around the central carbon atom.
That is, the color characteristics are not affected and the heat resistance can be improved. Thereby, the color filter formed using the coloring resin composition containing the coloring material of this invention is excellent in heat resistance.

(In the above general formula (I), [Z] ^m- represents an arbitrary m-valent anion.
R ^{1 to} R ⁶ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. When R ^{1 to} R ⁶ represent an alkyl group which may have a substituent, adjacent R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ are bonded to form a ring structure. It may be.

X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.
Y each independently represents a hydrogen atom or an arbitrary substituent.
In addition, multiple molecules in one molecule

May be the same structure or different structures.
m represents an arbitrary natural number. )
In general formula (I), R ^{1 to} R ⁶ may be the same or different. Therefore, the —NRR (RR represents any combination of R ¹ R ² , R ³ R ⁴ , and R ⁵ R ⁶ ) group may be left-right symmetric or left-right asymmetric.

When adjacent Rs (R represents any one of R ^{1 to} R ⁶ ) are bonded to form a ring, these may be a ring bridged with a heteroatom. Specific examples of this ring include the following. These rings may have a substituent.

R ^{1 to} R ⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent from the viewpoint of chemical stability. It is preferable.
Among them, R ^{1 to} R ⁶ are each independently a hydrogen atom;
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group;
It is more preferably any one of aryl groups such as a phenyl group, a naphthyl group, a thienyl group, a furyl group, and a thiazolyl group.

When R ^{1 to} R ⁶ represent an alkyl group or an aryl group, the alkyl group or aryl group may further have an arbitrary substituent.
Examples of the optional substituent that the alkyl group or aryl group may further have include the following [Substituent group Z].
[Substituent group Z]
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, Alkyl groups such as 2-ethylhexyl group, nonyl group, decyl group;
Aryl groups such as phenyl, naphthyl, thienyl, furyl, thiazolyl;
Halogen atoms such as fluorine atoms and chlorine atoms;
A cyano group;
Hydroxyl group;
Alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group;
An amino group optionally having a substituent such as an amino group, a diethylamino group, a dibutylamino group, an acetylamino group;
Acyl groups such as acetyl and benzoyl groups;
Acyloxy groups such as acetyloxy group and benzoyloxy group;
Etc.

As R < ¹ > -R < ⁶ >, the C1-C10 alkyl group which may have a substituent is still more preferable, More specifically, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, unsubstituted alkyl groups such as sec-butyl group, pentyl group, hexyl group, 2-ethylhexyl group;
An alkoxyalkyl group such as a 2-methoxyethyl group or a 2-ethoxyethyl group;
Acyloxy groups such as 2-acetyloxyethyl groups;
A cyanoalkyl group such as a 2-cyanoethyl group;
Examples thereof include fluoroalkyl groups such as 2,2,2-trifluoroethyl group and 4,4,4-trifluorobutyl group.

Among them, at least one of R ^{1 to} R ⁶ is a fluorine atom-containing group.
It is particularly preferable from the viewpoint that the heat resistance of the resulting color filter is improved by the intermolecular interaction between the positive charge present at the central carbon atom in the formula (I) and the fluorine atom-containing group. An aryl group, a fluoroalkyl group, etc. are mentioned, More preferably, it is a fluoroalkyl group.

That is, at least one of R ^{1 to} R ⁶ is preferably a hydrogen atom from the viewpoint of improving heat resistance by forming an intermolecular hydrogen bond. In addition, it is preferable that at least one of R ^{1 to} R ⁶ is a fluoroalkyl group having 1 to 10 carbon atoms from the viewpoint of improving heat resistance by having hydrophobicity, more preferably R ¹ and R ^2. (Or R ³ and R ⁴ ) is preferably a fluoroalkyl group having 1 to 10 carbon atoms.

In addition, carbon number of the said fluoroalkyl group is 1-10 normally, Preferably it is 2-8, More preferably, it is 4-6.
Within the above range, the hydrophobicity is moderate and this is preferable in terms of improving heat resistance.
X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom;
Methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, An alkyl group having 1 to 8 carbon atoms such as a 2-ethylhexyl group is shown.

When X is the above alkyl group, it may further have an arbitrary substituent. Examples of these substituents include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and propoxy group.
Specific examples of X include a haloalkyl group such as a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, and a 2,2,2-trifluoroethyl group; an alkoxyalkyl group such as a methoxymethyl group.

X is preferably a substituent having an appropriate steric hindrance such as a methyl group, a chlorine atom, or a trifluoromethyl group that does not affect the twist. X is most preferably a methyl group from the viewpoint of heat resistance.
Y may be any group as long as the effects of the present invention are not impaired. For example, hydrogen atom, methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl An alkyl group having 1 to 8 carbon atoms such as a group, sec-butyl group, tert-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group;
Alkoxy groups having 1 to 8 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group;
Halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;
A cyano group etc. are mentioned.

The alkyl group and alkoxy group may further have other optional substituents. Examples of other optional substituents include an alkoxy group. In addition, adjacent Y may combine to form a ring structure.
Y in the present invention is most preferably a hydrogen atom in terms of high color purity.
[Z] ^m- represents an arbitrary m-valent anion.

[Z] ^m- includes, for example, halide ions such as F ⁻ , Cl ⁻ , Br ⁻ and I ⁻ ;
_{(C 6 H 5) 4 B} - like boron anion;
Carboxylic acid anions such as CH ₃ COO ⁻ , C ₂ H ₅ COO ⁻ , C ₆ H ₅ COO ⁻ ;
Sulfate anions such as SO ₄ ²⁻ and HSO ₄ ⁻ ;
Phosphate anions such as HPO ₄ ²⁻ and PO ₄ ³⁻ ;
Examples include sulfonate anions.

Examples of the sulfonic acid anion include trifluoromethanesulfonic acid, methanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, dodecanesulfonic acid, camphorsulfonic acid and other aliphatic sulfones which may have a substituent. Acid anion;
An aromatic sulfonate anion which may have a substituent such as benzenesulfonic acid, p-toluenesulfonic acid, 1-naphthalenesulfonic acid, 2-naphthalenesulfonic acid;
acid blue 80 (C.I. 61585), acid green 25 (C.I. 61570), acid blue 45 (C.I. 63010), acid bl
an anion of an anthraquinone dye having a sulfonate group such as ue 43 (C.I.63000), acid blue 25 (C.I.62055), acid blue 40 (C.I.65125);
anions of phthalocyanine dyes having a sulfonate group such as direct blue 86 (C.I. 74810), direct blue 199 (C.I. 14190);
and an anion of an indigo dye having a sulfonate group such as acid blue 74 (C.I. 73015).

Moreover, when [Z] ^m- is an anion of a dye, it is preferably a blue dye.
In general formula (I), m represents an arbitrary natural number. From the viewpoint of color tone, m is preferably 1 to 4, more preferably 1 or 2.
Further, in the general formula (I), a plurality of

Are included, they may have the same structure or different structures, but the same structure is preferable from the viewpoint of easy production.
The dye represented by the general formula (I) can be synthesized by reacting the corresponding benzophenone body and the corresponding aminonaphthalene body with a chlorinating agent such as phosphorus oxychloride when X is a chlorine atom. As conditions for this reaction, for example, the contents described in “Review Synthetic Dyes” (Horiguchi Hiroshi, Sankyo Publishing, 1968) can be referred to. Also, benzophenone and aminonaphthalene can be synthesized by a combination of known reactions.

On the other hand, when X is other than a chlorine atom, for example, it can be synthesized by subjecting a corresponding dye in which X is a chlorine atom to a salt exchange reaction.
In the compound represented by the general formula (I), when focusing on the cation structure, two Ys at the ortho position of the benzene ring not having the substituent X are hydrogen and having no optional substituent ( That is, the compound represented by the following general formula (i) is considered to have a better color because the planar structure of the two benzene rings is maintained.

  In view of relatively easy production, among the compounds represented by the general formula (I) in the present invention, compounds represented by the following general formula (i) are particularly preferred.

(R ^{1 to} R ⁶ , X, Y, Z, and m in the general formula (i) are the same as those in the general formula (I).)
On the other hand, focusing on the anion structure, the compound represented by the following general formula (ii) is preferable because the compound represented by the general formula (I) can improve both heat resistance and light resistance.

(In the general formula (ii) above,
R ³¹ represents a hydrogen atom or a phenyl group which may have a substituent,
R ^{32 to} R ³⁴ each independently represent a hydrogen atom, a hydroxyl group, —NHR ⁴¹ (R ⁴¹ has the same meaning as R ³¹ ), —SO ₃ ^— , a halogen atom, —CO ₂ R ⁴² (R ⁴² represents carbon. Represents an alkyl group represented by formulas 1 to 3, and at least one of R ^{32 to} R ³⁴ is a —NHR ⁴¹ group.

R ^{35 to} R ³⁸ are each independently a hydrogen atom, —SO ₃ ^— , a halogen atom, a phenoxy group, a naphthyloxy group, an alkoxyl group having 1 to 12 carbon atoms, —CO ₂ R ⁴³ , a phenyl group, —SO ₃ R. ⁴⁴ or —SO ₂ NHR ⁴⁵ (wherein R ^{43 to} R ⁴⁵ each independently represents an alkyl group having 1 to 6 carbon atoms).
Further, m —SO ₃ ^— groups are bonded in one anthraquinone skeleton.

Note that m, R ^{1 to} R ⁶ , X, and Y are as defined in general formula (I).
Furthermore, when a plurality of cationic skeletons specified in the general formula (ii) are contained in one molecule, they may have the same structure or different structures. )
When attention is paid to the anion structure, the compound represented by the following general formula (iii ') is preferable as the compound represented by the general formula (I) in that heat resistance and high luminance (high transmittance) are obtained. .

(R ²⁰¹ represents an aliphatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.
R ^{1 to} R ⁶ , X, and Y are as defined in the above formula (i). )
R ²⁰¹ represents an aliphatic hydrocarbon ring having 6 to 20 carbon atoms which may have a substituent.
The carbon number of the aliphatic hydrocarbon ring in R ²⁰¹ is usually 6 to 20, preferably 6 to 16, and more preferably 8 to 12.

Within the above range, it is preferable in that the synthesis is relatively easy.
In addition, examples of the substituent that the aliphatic hydrocarbon ring in R ²⁰¹ may have include those described in the above [Substituent group Z] section.
In addition, the compound represented by the general formula (iii ′) is more specifically a compound represented by the following general formula (iii) in terms of heat resistance and high luminance (high transmittance). preferable.

(In the general formula (iii), R ^{1 to} R ⁶ , X, and Y have the same meanings as in the general formula (I).)
Furthermore, when paying attention to the anion structure, as the compound represented by the general formula (I), a compound represented by the following general formula (iv ′) is preferable in terms of heat resistance and high luminance (high transmittance).

(In the said general formula (iv '), R < ¹ > -R < ⁶ >, X, and Y are synonymous with the said general formula (I).
R ^{401 to} R ⁴⁰⁵ each independently represent a hydrogen atom, a halogen atom, a phenoxy group, a naphthyloxy group, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 6 carbon atoms.

However, among R ^{401 to} R ⁴⁰⁵ , at least one pair adjacent to each other is bonded to each other to form a ring that may have a substituent. )
R ^{401 to} R ⁴⁰⁵ each independently represent a hydrogen atom, a halogen atom, a phenoxy group, a naphthyloxy group, an alkoxyl group having 1 to 12 carbon atoms, a phenyl group, or an alkyl group having 1 to 6 carbon atoms.

However, among R ^{401 to} R ⁴⁰⁵ , at least one pair adjacent to each other is bonded to each other to form a ring that may have a substituent.
That is, at least one of R ⁴⁰¹ and R ⁴⁰² , R ⁴⁰² and R ⁴⁰³ , R ⁴⁰³ and R ⁴⁰⁴ , and R ⁴⁰⁴ and R ⁴⁰⁵ are bonded to each other to form a ring.
Preferable specific examples of the ring formed by bonding at least one adjacent pair of R ^{401 to} R ⁴⁰⁵ with each other include, for example, the following, but the present invention is not limited thereto. .

Among the above, among R ^{401 to} R ⁴⁰⁵ , adjacent pairs are bonded to each other to form a naphthalene ring together with the benzene ring in the formula, thereby linking the negative charge existing on the sulfonic acid to a conjugated system. It is preferable that the anion can be stabilized by being dispersed by extending the length, thereby improving the heat resistance.
In addition, among R ^{401 to} R ⁴⁰⁵ , examples of the substituent that may be included in the ring formed by bonding a pair of adjacent ones include those listed in the above [Substituent group Z] section. It is done.

  The compound represented by the general formula (iv ') is preferably a compound represented by the following general formula (iv) in terms of heat resistance and high luminance (high transmittance).

(In the general formula (iv), R ^{1 to} R ⁶ , X, and Y have the same meanings as in the general formula (I).)
When paying attention to both the anion structure and the cation structure, the compound represented by the general formula (ii) is more preferable as the compound represented by the general formula (I) in the present invention. Among them, the compound represented by the following general formula (v) is preferable from the viewpoint of improving heat resistance by stabilizing anions and improving light resistance by energy transfer.

(In the general formula (v), m, Y, R ^{1 to} R ⁵ , and R ^{31 to} R ³⁸ have the same meanings as in the general formula (ii).
Moreover, it is particularly preferable that at least one of R ^{1 to} R ⁵ is a fluorine atom-containing group or a branched alkyl group. More specifically, for example, a fluoroalkyl group or an isobutyl group can be mentioned.

In addition, when two or more cation skeletons of the said general formula (v) are contained in 1 molecule, they may be the same structure or a different structure. )
In the present invention, the electronic effect can be appropriately controlled by setting the cation skeleton of the compound represented by the general formula (v) to a structure represented by the following general formula. In addition, since two benzene rings bonded to —NR ¹ R ² and —NR ³ R ⁴ are considered to be equivalent in structure, one of the four ortho positions of the two benzene rings is a methyl group. It only needs to be replaced.

For the reasons described above, it can be presumed that a compound having a structure (cation skeleton) represented by the following formula is hardly affected by light, heat, etc. and also has good heat resistance while maintaining its color. For this reason, it is considered that such a compound is optimally used for the colored resin composition for a color filter of the present invention.
Furthermore, the compound in which R ⁶ in the general formula (I) is a hydrogen atom is preferable in terms of easy production.

  In addition, the compound represented with the said general formula (I) is necessarily obtained as a mixture of the multiple types of compound from which the value of m differs from the manufacturing process. In the color filter colored resin composition of the present invention, the compound represented by the general formula (I) may be used as a mixture or may be an isolated single compound. In the case of a mixture, the compound satisfying the above-mentioned “preferred” m value is preferably a mixture that occupies the largest proportion.

  Specific examples of the cation skeleton of the compound represented by the general formula (I) include the following structures, but the present invention is not limited to these as long as the gist thereof is not exceeded.

In the colored resin composition of the present invention, the content of the compound represented by the general formula (I) is usually 5% by weight or more based on the total amount of the color material (a). Preferably it is 20 weight% or more, More preferably, it is 30 weight% or more, Most preferably, it is 40 weight% or more.
Within the above range, it is preferable in that the effect of the present invention can be obtained satisfactorily.
In addition, when the solubility of the compound represented by the general formula (I) in the colored resin composition (especially the solvent contained in the composition) is low, the same as the optional component pigment described later. Alternatively, it may be used after being dispersed in the composition using a dispersant or the like.

However, from the viewpoint of high contrast when applied to a liquid crystal display device, the compound represented by the general formula (I) is preferably present in a dissolved state in the colored resin composition.
Further, the colored resin composition of the present invention may contain only one kind of the compound represented by the general formula (I) as the coloring material (a), or two or more kinds. In addition, one or more of other coloring materials may be included, but the content ratio of all (a) coloring materials in the colored resin composition of the present invention is based on the total solid content. Usually, it is 1 to 50% by weight, preferably 3 to 40% by weight, more preferably 5 to 30% by weight.

By setting the content of all (a) color materials in the above range, it is possible to prevent the color reproducibility from deteriorating or the film thickness from becoming too thick (when trying to obtain a desired color density). . Furthermore, various problems in plate making can be solved, and a film having higher strength can be obtained.
<(B) Solvent>
(B) In the colored resin composition of the present invention, the solvent (b) functions to adjust viscosity by dissolving or dispersing (a) the color material and (c) the binder resin and other components added in some cases. Have

(B) The solvent is not particularly limited as long as it can dissolve or disperse each component.
Examples of the solvent (b) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether. , Propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3- Methyl-3-methoxybutanol, Triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Mono- or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol;
aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionic acid Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Examples thereof include nitriles such as acetonitrile and benzonitrile.

  Commercially available solvents corresponding to the above include mineral spirit, Barsol # 2, Apco # 18 Solvent, Apco thinner, Soal Solvent No. 1 and no. 2, Solvesso # 150, Shell TS28 Solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all trade names) and the like. These solvents may be used alone or in combination of two or more.

<When forming color filter pixels by photolithography>
When forming pixels of a color filter by photolithography, a solvent having a boiling point in the range of 100 to 200 ° C. (under a pressure of 101.25 [hPa]. The same applies to the boiling point hereinafter) is selected. Is preferred. More preferably, it has a boiling point of 120-170 ° C. By controlling the boiling point within the above range, traces of bubbles may remain and become defects, or drying may not be completed within a predetermined time, causing problems such as color unevenness in the pixels. Can be prevented.

Glycol alkyl ether acetates are preferred from the standpoints of good balance of coating properties, surface tension, and the like in the solvent, and relatively high solubility of the components in the composition.
The glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferable. Of these, propylene glycol monomethyl ether is particularly preferred because of the solubility of the constituent components in the composition. Glycol monoalkyl ethers are highly polar, and if the amount added is too large, the pigment tends to aggregate, and the storage stability such as the viscosity of the colored resin composition obtained later tends to decrease. The proportion of glycol monoalkyl ethers in the solvent is preferably 5% by weight to 30% by weight and more preferably 5% by weight to 20% by weight in the whole solvent.

  It is also preferable to use a solvent having a boiling point of 150 ° C. or higher. By using such a high boiling point solvent in combination, the colored resin composition becomes difficult to dry, but it has the effect of making it difficult for the pigment dispersion liquid to break down due to rapid drying. The content of the high boiling point solvent is preferably 3% by weight to 50% by weight, more preferably 5% by weight to 40% by weight, and particularly preferably 5% by weight to 30% by weight with respect to the whole solvent. If the amount of the high-boiling solvent is too small, for example, the coloring material component may precipitate and solidify at the tip of the slit nozzle and cause foreign matter defects, and if it is too much, the drying speed of the composition will be slowed down. In the filter manufacturing process, there may be a tact defect in the vacuum drying process and a pin mark of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
<When forming color filter pixels by inkjet method>
When forming a pixel of a color filter by the ink jet method, a solvent having a boiling point of usually 130 ° C. or higher and 300 ° C. or lower, preferably 150 ° C. or higher and 280 ° C. or lower is appropriate. When the boiling point is too low, the uniformity of the resulting coating film tends to be poor. Conversely, if the boiling point is too high, as described later, the effect of inhibiting the drying of the colored resin composition is high, but there are many residual solvents in the coating film even after thermal firing, causing problems in quality, In some cases, the drying time in vacuum drying or the like becomes long, resulting in problems such as an increase in tact time.

The solvent vapor pressure is usually 10 mmHg or less, preferably 5 mmHg or less, more preferably 1 mmHg or less, from the viewpoint of the uniformity of the resulting coating film.
In addition, in the production of color filters by the inkjet method, the ink emitted from the nozzle is very fine, several to several tens of pL, so the solvent evaporates and concentrates before landing on the periphery of the nozzle mouth or in the pixel bank.・ Tends to dry. In order to avoid this, it is preferable that the solvent has a high boiling point. Specifically, it is preferable to include a solvent having a boiling point of 180 ° C. or higher. More preferably, it contains a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. Further, the high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by weight or more, more preferably 70% by weight or more, in the whole solvent contained in the colored resin composition for a color filter of the present invention. 90% by weight or more is most preferable. When the high boiling point solvent is less than 50% by weight, the effect of preventing evaporation of the solvent from the droplets may not be sufficiently exhibited.

Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, and 1,6-hexanol diester. Examples include acetate and triacetin.
Furthermore, it is also effective to partially contain a solvent having a boiling point lower than 180 ° C. in order to adjust the viscosity of the pigment dispersion or the colored resin composition and the solubility of the solid content. As such a solvent, a solvent having low viscosity, high solubility, and low surface tension is preferable, and ethers, esters, ketones, and the like are preferable. Of these, cyclohexanone, dipropylene glycol dimethyl ether, cyclohexanol acetate, and the like are particularly preferable.

On the other hand, when the solvent contains alcohols, the ejection stability in the ink jet method may deteriorate. Therefore, the alcohol is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less in the entire solvent.
The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by weight or less. When the solvent exceeds 99% by weight, (a) the color material, (c) the binder resin, etc. are too small to form a coating film. On the other hand, the lower limit of the solvent content is usually 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more in consideration of viscosity suitable for coating.

<(C) Binder resin>
The (c) binder resin used in the colored resin composition of the present invention can be used without particular limitation as long as it can be used for a color filter.
For example, a thermosetting resin composition used in a so-called lift-off type color filter manufacturing process described in JP-A-60-184202 and the like, and an inkjet type color filter manufacturing described in JP-A-2004-220036 Examples thereof include a thermosetting resin composition used in the process and a photopolymerizable resin composition described later. A suitable type of resin composition may be selected depending on the means by which the colored resin composition is cured to produce a color filter. When the colored resin composition is a photopolymerizable composition, it preferably contains photopolymerization initiators described later.

As described later, the colored resin composition of the present invention is preferably used for the production of a color filter by a photolithography method or an inkjet method, and is photopolymerizable (in the case of a photolithography method or an inkjet method) or thermosetting. It is preferable that it is a property (inkjet system).
Hereinafter, although the case where the colored resin composition of the present invention is a photopolymerizable resin composition and the case of being a thermosetting resin composition will be described in detail, the present invention is not limited thereto. .

When the colored resin composition of the present invention is a photopolymerizable resin composition, examples of the (c) binder resin include JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, and JP-A-11. It is possible to use known polymer compounds described in various publications such as JP-A No. 140144, JP-A No. 11-174224, JP-A No. 2000-56118, JP-A No. 2003-233179, and JP-A No. 2007-270147. Preferably, an ethylenically unsaturated group-containing monomer containing (c-1): mono (meth) acrylate having a specific structure, and epoxy group-containing (meth) acrylate or (meth) acrylic acid. (Meth) acrylic alkali-soluble resin obtained by reaction,
(C-2): a linear alkali-soluble resin containing a carboxyl group in the main chain,
(C-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the carboxyl group-containing resin,
(C-4): (Meth) acrylic resin and the like.

Especially, (c-1) resin is especially preferable from points, such as solubility and photocurability.
Hereinafter, each of these resins will be described.
<(C-1): obtained by reacting a monomer containing an ethylenically unsaturated group containing a mono (meth) acrylate having a specific structure and an epoxy group-containing (meth) acrylate or (meth) acrylic acid (Meth) acrylic alkali-soluble resin>
Among the (c) binder resins used in the colored resin composition of the present invention, as one of the particularly preferred (c) binder resins, “copolymer of epoxy group-containing (meth) acrylate and other radical polymerizable monomer is used. A resin obtained by adding an unsaturated monobasic acid to at least a part of the epoxy group of the copolymer, or a polybasic acid anhydride is added to at least a part of the hydroxyl group generated by the addition reaction. Resin obtained by the above process (hereinafter sometimes referred to as (c-1) resin) ”.

More specifically, as the (c-1) resin, for example, a (meth) acrylic copolymer (c-) using a mono (meth) acrylate having a specific alicyclic hydrocarbon group described below. 1-1) to (c-1-3) are preferable. Among these, the (meth) acrylic copolymer described in the following (c-1-2) is more preferable from the viewpoint of solubility.
<(C-1-1) (A) Mono (meth) acrylate having a structure represented by the following general formula (7) and (B) an ethylenically unsaturated group-containing unit containing an epoxy group-containing (meth) acrylate (Meth) acrylic copolymer obtained by reacting a monomer (hereinafter sometimes referred to as (c-1-1) copolymer)>
(C-1-1) The copolymer contains (A) a partial structure derived from mono (meth) acrylate having a structure represented by the following general formula (7) as an essential component.

In the general formula (7), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Especially, as a structure represented by General formula (7), what is represented by following Structural formula (7a), (7b), or (7c) is preferable.

In addition, the mono (meth) acrylate which has a structure represented by the said General formula (7) may be used individually by 1 type, and may use 2 or more types together.
In addition, as the mono (meth) acrylate having the structure represented by the general formula (7), various known ones can be used as long as the structure has the structure, and particularly represented by the following general formula (8). Those are preferred.

In the general formula (8), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the general formula (7).
The (c-1-1) copolymer has a partial structure derived from (B) an epoxy group-containing (meth) acrylate (hereinafter sometimes referred to as (B1) an epoxy group-containing (meth) acrylate) as an essential component. And

  (B1) Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, and 4-hydroxybutyl. Examples include (meth) acrylate glycidyl ether. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

In addition, (A) mono (meth) acrylate having a structure represented by the general formula (7),
b1) A known solution polymerization method is applied to the copolymerization reaction with the epoxy group-containing (meth) acrylate. The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used.
The usage-amount of a solvent is 30-1000 weight part normally with respect to 100 weight part of copolymers to be obtained (c-1-1), Preferably it is 50-800 weight part. If the amount of the solvent used is outside this range, it will be difficult to control the molecular weight of the copolymer.

The radical polymerization initiator used in the copolymerization reaction is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound catalyst is used. be able to.
Among radical polymerization initiators using an organic peroxide catalyst or an azo compound catalyst, one or more radical polymerization initiators having an appropriate half-life are used depending on the polymerization temperature. The usage-amount of a radical polymerization initiator is 0.5-20 weight part with respect to a total of 100 weight part of the monomer used for a copolymerization reaction, Preferably it is 1-10 weight part.

  The copolymerization reaction may be performed by dissolving the monomer and radical polymerization initiator used in the copolymerization reaction in a solvent and raising the temperature while stirring, or by adding the monomer to which the radical polymerization initiator is added. Alternatively, the reaction may be performed dropwise in a solvent that has been heated and stirred. Alternatively, the monomer may be added dropwise while the radical polymerization initiator is added to the solvent and the temperature is raised. The reaction conditions can be freely changed according to the target molecular weight.

The copolymer obtained by reacting (A) the mono (meth) acrylate having the structure represented by the general formula (7) and (B1) the epoxy group-containing (meth) acrylate as the essential components described above is Furthermore, (E) it may contain other monomer-derived partial structures.
(E) There is no restriction | limiting in particular as another monomer, What is necessary is just a compound which can be copolymerized with (A), (B1), and (B2) (meth) acrylic acid.

Specifically, for example, vinyl aromatics such as styrene, styrene α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives; butadiene, 2,3-dimethylbutadiene, isoprene, Dienes such as chloroprene; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid-iso-propyl, (meth) acrylic acid-n-butyl, (Meth) acrylic acid-sec-butyl, (meth) acrylic acid-tert-butyl, (meth) acrylic acid pentyl, (meth) acrylic acid neopentyl, (meth) acrylic acid isoamyl, (meth) acrylic acid hexyl, (meta ) -2-ethylhexyl acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, (meth) acrylic Cyclopentyl acid, cyclohexyl (meth) acrylate, (meth) acrylate-2-methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, propargyl (meth) acrylate, ( (Meth) acrylic acid phenyl, (meth) acrylic acid naphthyl, (meth) acrylic acid anthracenyl, (meth) acrylic acid anthraninonyl, (meth) acrylic acid piperonyl, (meth) acrylic acid salicylate, (meth) acrylic acid furyl, (Meth) acrylic acid furfuryl, (meth) acrylic acid tetrahydrofuryl, (meth) acrylic acid pyranyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl, (meth) acrylic acid cresyl, (meth) acrylic acid-1 , 1,1-trifluoro Ethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, (Meth) acrylic acid esters such as (meth) acrylic acid 3- (N, N-dimethylamino) propyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl; ) Acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N- (Meth) acrylic amides such as di-iso-propylamide, (meth) acrylic acid anthracenyl amide; Vinyl compounds such as anilide luric acid, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate; diethyl citraconic acid, diethyl maleate, Unsaturated dicarboxylic acid diesters such as diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide and N- (4-hydroxyphenyl) maleimide; N- (meta ) Acrylyl phthalimide and the like.

(E) Among other monomers, in order to impart excellent heat resistance, coating strength, and pigment dispersibility to the colored curable resin composition, (such as styrene, benzyl (meth) acrylate) E1) An ethylenically unsaturated monomer having an aromatic hydrocarbon group is preferred.
When the partial structure derived from this (E1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the (c-1-1) copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.

<(C-1-2) (A) A mono (meth) acrylate having a structure represented by the general formula (7), and (B1) an ethylenically unsaturated group-containing unit containing an epoxy group-containing (meth) acrylate Polymers are obtained to obtain a trunk resin, (C) an unsaturated monobasic acid is reacted with at least part of the epoxy group derived from (B1) in the trunk resin, and (D) A (meth) acrylic copolymer obtained by reacting a polybasic acid or an anhydride thereof. >
In the present invention, the resin (c-1) that can be used is the above-mentioned “(A) mono (meth) acrylate having the structure represented by the general formula (7) and (B1) epoxy group-containing (meth) acrylate”. (And (E) other monomer as required) (C) Unsaturated at least part of the epoxy group derived from (B1) of the (meth) acrylic copolymer obtained by reacting A copolymer (hereinafter referred to as (c-1-2) copolymer) obtained by reacting a monobasic acid and reacting (D) a polybasic acid anhydride with at least a part of the generated hydroxyl group. It may be.

  (C) As unsaturated monobasic acid, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned. Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, or a cyano group. And monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferred. These (C) unsaturated monobasic acids may be used alone or in combination of two or more. By adding such components, it is possible to impart polymerizability to the (c) binder resin used in the present invention.

  These (C) unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group derived from (B1) in the copolymer, preferably 30 to 100 mol%, more preferably 50 to 50 mol%. Add to 100 mol%. (C) If the addition ratio of unsaturated monobasic acid is too small, wetting and spreading may be insufficient. In addition, a well-known method is employable as a method of adding (C) unsaturated monobasic acid to the epoxy group of a copolymer.

Further, when (C) an unsaturated monobasic acid is added to the epoxy group derived from (B1), a known one can be used as the (D) polybasic acid or anhydride thereof added to the resulting hydroxyl group. For example, dibasic acids such as maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, chlorendic acid; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid Examples of the acid include bases or higher and anhydrides thereof.

  Of these, acid anhydrides are preferable, and tetrahydrophthalic anhydride and / or succinic anhydride are particularly preferable. These (D) polybasic acids or anhydrides thereof may be used alone or in combination of two or more. By adding such components, it is possible to impart alkali solubility to the (c) binder resin used in the colored resin composition of the present invention, and (c) wetting and spreading properties to the binder resin and adhesion to the substrate. Can also be given. In addition, when manufacturing an ink-jet color filter, the wettability of the composition (in the pixel formation area surrounded by the black matrix in the pixel bank) (hereinafter simply referred to as “wet spreadability of the composition”). Can be expected to improve.

  These (D) polybasic acids or anhydrides thereof are usually 10 to 100 of hydroxyl groups generated by adding (C) unsaturated monobasic acid to the epoxy group derived from (B1) of the copolymer. Although it is made to add to mol%, Preferably it is added to 20-90 mol%, More preferably, it is added to 30-80 mol%. Adjustment of the addition ratio in this range is considered to be effective in controlling the wet spreadability of the composition. If the addition ratio is too small, there is a possibility that the effect of improving spreadability and the effect of improving adhesion cannot be sufficiently exhibited. On the other hand, if the addition ratio is too large, the remaining film ratio during development may be reduced. In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.

  Furthermore, when the colored resin composition of the present invention is a photopolymerizable composition, in order to improve the sensitivity to light, after adding the above-mentioned polybasic acid anhydride, one of the generated carboxyl groups is added. Glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group may be added to the part. Moreover, in order to improve developability, you may add the glycidyl ether compound which does not have a polymerizable unsaturated group to some produced | generated carboxyl groups. Both of these may be added.

  Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include glycidyl ether compounds having a phenyl group or an alkyl group. As commercial products, for example, trade names “Denacol EX-111”, “Denacol EX-121”, “Denacol EX-141”, “Denacol EX-145”, “Denacol EX-146”, “Denacol EX-146” manufactured by Nagase Chemical Industries, Ltd. Denacol EX-171 "," Denacol EX-192 "and the like.

  In addition, the trunk resin in the (c-1-2) copolymer also has a partial structure derived from the above-mentioned (E) other monomer as in the (c-1-1) copolymer. You may do it. (E) Examples of other monomers include the same compounds as in the (c-1-1) copolymer. Also preferred are ethylenically unsaturated monomers having (E1) aromatic hydrocarbons such as styrene and benzyl (meth) acrylate.

<(C-1-3) (A) Monoethyl (meth) acrylate having a structure represented by the general formula (7), and (B2) ethylenically unsaturated group-containing monomer containing (meth) acrylic acid (Meth) acrylic copolymer obtained by reacting
In the present invention, (c) resin that can be used as (c) binder resin is (A) mono (meth) acrylate having the structure represented by the general formula (7), and (B2) (meth) acrylic. Even a (meth) acrylic copolymer (hereinafter sometimes referred to as (c-1-3) copolymer) obtained by reacting an ethylenically unsaturated group-containing monomer containing an acid. Good.

The (c-1-3) copolymer may also have a partial structure derived from the above-mentioned (E) other monomer, similarly to the (c-1-1) copolymer. (E) Other monomers include the same compounds as described in the section of (c-1-1) copolymer, and among them, (E1) aromatics such as styrene and benzyl (meth) acrylate Ethylenically unsaturated monomers having hydrocarbons are preferred.

When the partial structure derived from this (E1) ethylenically unsaturated monomer having an aromatic hydrocarbon group is contained in the (c-1-3) copolymer, the content is 1 to 70 mol%. Some are preferred, and more preferably 3 to 50 mol%.
In addition, it is preferable that the polystyrene equivalent weight average molecular weight (Mw) measured by GPC of (c-1) resin used for the colored resin composition of this invention is 3000-100000, and is 4000-50000. It is more preferable. If the molecular weight is less than 3000, heat resistance and film strength may be inferior, and if it exceeds 100,000, the solubility in a developer tends to be insufficient. Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

Moreover, the acid value of (c-1) resin used for the colored resin composition of this invention is 0-200 mgKOH / g normally, Preferably it is 0-150 mgKOH / g, More preferably, it is 0-100 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
Furthermore, when the resin (c-1) used in the colored resin composition of the present invention contains an epoxy group, the epoxy equivalent is preferably 150 or more and 400 or less, more preferably 150 or more and 350 or less. preferable. When the epoxy equivalent is too low, there is a possibility that the effect of suppressing the decrease in luminance due to the oxidation of the resin is reduced. On the other hand, if it is too high, the number of double bonds, which are functional groups for photopolymerization, decreases, and the sensitivity may be lowered.

<(C-2) Linear Alkali-Soluble Resin Containing a Carboxyl Group in the Main Chain (hereinafter, referred to as “(c-2) Resin”)>
(C-2) The linear alkali-soluble resin containing a carboxyl group in the main chain is not particularly limited as long as it has a carboxyl group, and usually obtained by polymerizing a polymerizable monomer containing a carboxyl group. It is done.

  Examples of the carboxyl group-containing polymerizable monomer include (meth) acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, 2- (meth) acryloyloxyethyl succinic acid, and 2- (meth) acryloyloxyethyl adipic acid. 2- (meth) acryloyloxyethylmaleic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxypropylsuccinic acid, 2- ( (Meth) acryloyloxypropyladipic acid, 2- (meth) acryloyloxypropylmaleic acid, 2- (meth) acryloyloxypropylhydrophthalic acid, 2- (meth) acryloyloxypropylphthalic acid, 2- (meth) acryloyloxybutyl Succinic acid, 2- (me ) Vinyl monomers such as acryloyloxybutyl adipic acid, 2- (meth) acryloyloxybutylmaleic acid, 2- (meth) acryloyloxybutylhydrophthalic acid, 2- (meth) acryloyloxybutylphthalic acid; -Monomers obtained by adding lactones such as caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone; hydroxyalkyl (meth) acrylate to succinic acid, maleic acid, phthalic acid, or anhydrides thereof And monomers added with acids or anhydrides. A plurality of these may be used.

Among these, (meth) acrylic acid and 2- (meth) acryloyloxyethyl succinic acid are preferable, and (meth) acrylic acid is more preferable.
Moreover, (D-2) resin may copolymerize the other polymerizable monomer which does not have a carboxyl group with said carboxyl group-containing polymerizable monomer.
Other polymerizable monomers include, but are not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, benzyl (Meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, glycerol mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, tricyclodecanyl (meth) acrylate, isobonyl (meth) acrylate (Meth) acrylic acid esters such as adamantyl (meth) acrylate; vinyl aromatics such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-cyclohexylmaleimide, N-phenylmaleimide, N-benzyl N-substituted maleimides such as maleimide; macros such as polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer And monomers. These may be used in combination.

  Particularly preferred are styrene, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, They are butyl (meth) acrylate, isobutyl (meth) acrylate, tricyclodecanyl (meth) acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, and N-phenylmaleimide.

  The (c-2) resin used in the colored resin composition of the present invention may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, and the like. It is done. By copolymerizing these with the above-mentioned various monomers, a resin having a carboxyl group and a hydroxyl group can be obtained.

  Specific examples of the (c-2) resin that can be used in the colored resin composition of the present invention include (meth) acrylic acid, methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, Polymeric monomers not containing hydroxyl groups such as isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, etc. Of (meth) acrylic acid and methyl (meth) acrylate, benzyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-hydroxyethyl methacrylate, etc. )acrylic Copolymer of ester; Copolymer of (meth) acrylic acid and styrene; Copolymer of (meth) acrylic acid, styrene and α-methylstyrene; Copolymerization of (meth) acrylic acid and cyclohexylmaleimide Examples include coalescence. From the viewpoint of excellent pigment dispersibility, a copolymer resin containing benzyl (meth) acrylate is particularly preferable.

Moreover, the acid value of (c-2) resin used for the colored resin composition of this invention is 30-500 mgKOH / g normally, Preferably it is 40-350 mgKOH / g, More preferably, it is 50-300 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-20000 normally, Preferably it is 3000-50000, More preferably, it is 4000-30000. If the weight average molecular weight is too small, the stability of the colored composition tends to be inferior. If it is too large, the solubility in the developer tends to deteriorate.

<(C-3) Resin in which an epoxy group-containing unsaturated compound is added to the carboxyl group portion of the resin of (c-2) (hereinafter sometimes referred to as (c-3) resin>
A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the linear alkali-soluble resin containing a carboxyl group in the main chain (c-2) is also particularly preferable.
The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule.

  For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, N- (3,5-dimethyl-4-glycidyl) benzylacrylamide, 4- An acyclic epoxy group-containing unsaturated compound such as hydroxybutyl (meth) acrylate glycidyl ether can also be mentioned, but an alicyclic epoxy group-containing unsaturated compound is preferred from the viewpoint of heat resistance and pigment dispersibility.

  Here, as the alicyclic epoxy group-containing unsaturated compound, as the alicyclic epoxy group, for example, 2,3-epoxycyclopentyl group, 3,4-epoxycyclohexyl group, 7,8-epoxy [tricyclo [5 .2.1.0] dec-2-yl] group and the like. Further, the ethylenically unsaturated group is preferably derived from a (meth) acryloyl group, and suitable alicyclic epoxy group-containing unsaturated compounds are represented by the following general formulas (3a) to (3m). And the compounds represented.

In the general formulas (3a) to (3m), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents an alkylene group, R ¹³ represents a divalent hydrocarbon group, and n represents an integer of 1 to 10. is there.
In general formulas (3a) to (3m), the alkylene group for R ¹² preferably has 1 to 10 carbon atoms. Specific examples include a methylene group, an ethylene group, a propylene group, and a butylene group, and a methylene group, an ethylene group, and a propylene group are preferable.

As the hydrocarbon group R ^13, preferably has 1 to 10 carbon atoms, alkylene group, a phenylene group, and the like. These alicyclic epoxy group-containing unsaturated compounds may be used alone or in combination of two or more.
Among these, a compound represented by the general formula (3c) is preferable, and 3,4-epoxycyclohexylmethyl (meth) acrylate is particularly preferable.

  In order to add the epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (c-2), a known method can be used. For example, a carboxyl group-containing resin and an epoxy group-containing unsaturated compound are converted into a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyltriethylammonium chloride A quaternary ammonium salt such as pyridine, triphenylphosphine, etc., in an organic solvent at a reaction temperature of 50 to 150 ° C. for several hours to several tens of hours. Saturated compounds can be introduced.

The acid value of the carboxyl group-containing resin into which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g, more preferably 30 to 150 mgKOH / g. By controlling the acid value within these ranges, it is possible to prevent the solubility in the developer from decreasing or the film from being roughened.
Moreover, the weight average molecular weight of polystyrene conversion measured by GPC is 2000-100000 normally, Preferably it is 4000-50000, More preferably, it is 5000-30000. If the weight average molecular weight is too small, the stability of the colored composition tends to be inferior. If it is too large, the solubility in the developer tends to deteriorate.

<(C-4) (Meth) acrylic resin (hereinafter sometimes referred to as (c-4) resin>
Examples of the (meth) acrylic resin include a (c-4) resin obtained by polymerizing a monomer component essentially including a compound represented by the following general formula (9).

In the general formula (9), R ^1a and R ^2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
Hereinafter, the compound of the general formula (9) will be described in detail.
In the ether dimer represented by the general formula (9), the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ^1a and R ^2a is not particularly limited. Linear or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; substituted with alkoxy such as 1-methoxyethyl, 1-ethoxyethyl An alkyl group substituted with an aryl group such as benzyl. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl or the like, or a primary or secondary carbon substituent which is difficult to be removed by heat is preferable from the viewpoint of heat resistance. R ^1a and R ^2a may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 '-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2'-[oxybis (methylene)] bis-2-propeno , Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2 -Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1- Ethoxyethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis ( Methylene)] bis-2-propenoate, dicyclohexyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, di (t- Tilcyclohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tri Cyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 Examples include '-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, and the like.

  Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be used alone or in combination of two or more.

  The proportion of the ether dimer in the monomer component in obtaining the (c-4) resin is not particularly limited, but is usually 2 to 60% by weight, preferably 5 to 55% by weight, more preferably in all monomer components. Is 5 to 50% by weight. If the amount of the ether dimer is too large, it may be difficult to obtain a low molecular weight product during polymerization, or may be easily gelled. On the other hand, if the amount is too small, transparency, heat resistance, etc. The coating film performance may be insufficient.

(C-4) The resin preferably has an acid group. By having an acid group, the resulting colored resin composition can be cured by a crosslinking reaction in which an acid group and an epoxy group react to form an ester bond (hereinafter sometimes abbreviated as acid-epoxy curing). A colored resin composition, or a composition in which an uncured portion can be visualized with an alkali developer. The acid group is not particularly limited, and examples thereof include a carboxyl group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups contained in one molecule of resin may be only one kind or two or more kinds.

  (C-4) In order to introduce an acid group into a resin, for example, a monomer having an acid group, and / or a “monomer capable of imparting an acid group after polymerization” (hereinafter referred to as “monomer for introducing an acid group”) May be used as the monomer component. In addition, when using "monomer which can provide an acid group after superposition | polymerization" as a monomer component, the process for providing an acid group as mentioned later is required after superposition | polymerization.

Examples of the monomer having an acid group include monomers having a carboxyl group such as (meth) acrylic acid and itaconic acid; monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide; maleic anhydride and itaconic anhydride. Although the monomer etc. which have a carboxylic anhydride group are mentioned, Especially, (meth) acrylic acid is preferable among these.
Examples of the monomer capable of adding an acid group after the polymerization include monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate; monomers having an epoxy group such as glycidyl (meth) acrylate; 2-isocyanatoethyl (meta ) Monomers having an isocyanate group such as acrylate.

Only one type of monomer for introducing these acid groups may be used, or two or more types may be used.
(C-4) When the monomer component for obtaining the resin also includes the monomer for introducing the acid group, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer component, preferably Is from 10 to 60% by weight. By adjusting the amount of the monomer for introducing the acid group within this range, good electrical characteristics and developability can be obtained.

Moreover, (c-4) resin may have a radically polymerizable double bond.
In order to introduce a radical polymerizable double bond into the (c-4) resin, for example, “a monomer capable of imparting a radical polymerizable double bond after polymerization” (hereinafter referred to as “for introducing a radical polymerizable double bond”). May be referred to as a “monomer.”) As a monomer component, and then a treatment for imparting a radical polymerizable double bond as described later may be performed.

  Examples of the monomer capable of imparting a radical polymerizable double bond after polymerization include, for example, a monomer having a carboxyl group such as (meth) acrylic acid and itaconic acid; a carboxylic acid anhydride group such as maleic anhydride and itaconic anhydride Monomers: Monomers having an epoxy group such as glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. The monomer for introducing these radical polymerizable double bonds may be only one kind or two or more kinds.

  (C-4) When the monomer component for obtaining the resin also includes a monomer for introducing the radical polymerizable double bond, the content ratio is not particularly limited, but usually 5 to 70 in all the monomer components. % By weight, preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the radical polymerizable double bond within this range, good plate making characteristics can be obtained, and a pixel having a desired taper angle with little chipping can be obtained.

(C-4) The resin preferably has an epoxy group. In order to introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component.
Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

  (C-4) When the monomer component for obtaining the resin also includes a monomer for introducing the epoxy group, the content ratio is not particularly limited, but is usually 5 to 70% by weight in the total monomer component, preferably Is preferably 10 to 60% by weight. By adjusting the amount of the monomer for introducing the epoxy group within this range, the heat resistance and the like can be improved without deteriorating exposure sensitivity and color characteristics.

(C-4) The monomer component for obtaining the resin may contain other copolymerizable monomers, if necessary, in addition to the essential monomer component.
Examples of other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, methyl 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as; aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; butadienes such as butadiene and isoprene; Substituted butadiene compounds; ethylene, propylene, vinyl chloride , Ethylene or substituted ethylene compound such as acrylonitrile, vinyl esters such as vinyl acetate and the like.

  Among these, methyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and styrene are preferable in terms of good transparency and resistance to heat resistance. These other copolymerizable monomers may be used alone or in combination of two or more. When the monomer component for obtaining the (c-4) (meth) acrylic resin also contains the other copolymerizable monomer, the content ratio is not particularly limited, but is preferably 95% by weight or less, 85 More preferably, it is less than wt%. When there is too much content rate, developability may deteriorate.

  (C-4) The weight average molecular weight of the resin is not particularly limited, but the polystyrene equivalent weight average molecular weight measured by GPC is preferably 2,000 to 200,000, more preferably 4,000 to 100,000. When the weight average molecular weight exceeds 200,000, the viscosity may become too high to form a coating film, and when it is less than 2,000, sufficient heat resistance tends to be hardly exhibited.

(C-4) When resin has an acid group, a preferable acid value is 5-500 mgKOH / g, More preferably, it is 10-400 mgKOH / g. When the acid value is less than 5 mgKOH / g, it may be difficult to apply to alkali development. Moreover, when it exceeds 500 mgKOH / g, there exists a tendency for it to become high viscosity and to become difficult to form a coating film.
In addition, when an acid value is comparatively high, since it becomes difficult to produce the time-dependent change (thickening) of a viscosity of the colored resin composition containing this, when an acid value is comparatively low, the colored resin composition containing this is preferable. This is preferable because a change (decrease) in contrast with time is less likely to occur.

Further, (c-4) resins, that is, copolymers having a compound represented by the general formula (9) as an essential monomer component are disclosed in, for example, JP-A-2004-300203 and JP-A-2004-30020.
The compounds described in Japanese Patent No. 4 can be mentioned.
As the (c) binder resin of the present invention, for example, an acrylic resin described in JP-A-2005-154708 can also be used.

The colored resin composition of the present invention may contain a binder resin other than the above-mentioned (c-1) to (c-4) resins as long as the effects of the present invention are not impaired.
Moreover, as (c) binder resin used for the colored resin composition of this invention, 1 type may be used independently among the above-mentioned various resin, and 2 or more types may be used together.
Further, the content ratio of (c) binder resin is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, preferably 60% by weight or less in the total solid content. . (C) When there is too little content of binder resin, a film | membrane will become weak and the adhesiveness to a board | substrate may fall. On the other hand, when the amount is too large, the permeability of the developing solution to the exposed portion increases, and the surface smoothness and sensitivity of the pixel may deteriorate.

<Other ingredients>
The colored resin composition of the present invention may contain components other than those described above as necessary. Examples of such components include (d) pigments, (e) dispersants and dispersion aids, (f) polymerizable monomers, (g) photopolymerization initiators, and / or thermal polymerization initiators, and surfactants. , Thermal polymerization inhibitors, plasticizers, storage stabilizers, surface protective agents, adhesion improvers, development improvers and the like.

<(D) Pigment>
The colored resin composition of the present invention may further contain (d) a pigment as a coloring material, if necessary. Examples of the (d) pigment that can be used include pigments of various colors such as a red pigment, a blue pigment, a green pigment, a yellow pigment, a purple pigment, an orange pigment, and a brown pigment.
Examples of the chemical structure include organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, although the specific example of the pigment which can be used is shown by a pigment number, the pigment which can be used is not limited to these illustrations.

  First, as a red pigment, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276 and the like. Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, etc., more preferably C.I. I. Pigment red 177, 209, 224, 242, 254, and the like.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1
15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, and the like. Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, etc., more preferably C.I. I. Pigment blue 15: 4, 15: 6, and the like.

Examples of green pigments include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 and the like. Of these, C.I. I. Pigment green 7, 36, 58, and the like.
Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 215, and the like. Of these, C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, 215, etc., more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180, 215, and the like.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, pigment blue 80, and the like. Of these, C.I. I. Pigment violet 19, 23, etc., more preferably C.I. I. Pigment violet 23 and the like.

  Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 and the like. Of these, C.I. I. Pigment orange 38, 71 and the like.

Examples of the inorganic pigment include barium sulfate, lead sulfate, titanium oxide, yellow lead, red iron oxide, chromium oxide and the like.
The above various pigments can be used in combination. For example, in order to adjust the chromaticity, as the (d) pigment, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

When forming the resin black matrix of a color filter using the colored resin composition of this invention, a black pigment can be used. A black pigment may be used alone, or pigments such as red, green, and blue may be mixed and used. Further, it may be an inorganic pigment or an organic pigment.
Examples of black pigments that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, and titanium black. Among these, carbon black and titanium black are preferable from the viewpoints of light shielding rate and image characteristics.

The inorganic pigment and organic pigment used in the present invention have an average primary particle size of usually 100 nm or less, preferably 40 nm or less, more preferably 10 nm or more and 30 nm or less. Since the present invention is particularly effective in the case of a composition containing a highly atomized pigment, the case of containing a pigment having an average primary particle size of 10 nm to 30 nm is particularly preferable.
If the average primary particle size is too large, the depolarization characteristics will deteriorate and the contrast will be insufficient, and if it is severe, the transmittance will be lowered. In some cases, production problems may occur, such as generation of protruding foreign matter, decreasing the yield of the color filter, or causing the process filter to be blocked. On the other hand, if it is too small, problems such as a decrease in dispersion stability due to an increase in the specific surface area of the pigment and a deterioration in heat resistance and light resistance due to the pigment approaching the molecular state may occur.

  The primary particle size of the pigment can be determined by the following method. First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). In the case of organic pigments and titanium black pigments, a plurality of (usually about 200 to 300) pigment particles having a diameter equivalent to an area circle converted to the diameter of a circle having the same area as the particle diameter of each pigment particle. The particle diameter is determined for each of. Using the obtained primary particle size value, the number average value is calculated according to the following formula to obtain the average particle size.

In addition, it is also preferable to adjust the pigment content in the colored resin composition that forms each pixel of the color filter to be described later to an optimum range.
<(E) Dispersant and dispersion aid>
When the colored resin composition of the present invention further contains (d) a pigment as a coloring material, it may contain (e) a dispersant, a dispersion aid, and the like. As these components, for example, various compounds described in JP-A No. 2007-113000 can be used.

<(F) Polymerizable monomer>
(F) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”) is available. preferable. When the colored resin composition of the present invention is irradiated with actinic rays, the ethylenic compound is subjected to addition polymerization by the action of a photopolymerization initiation system described later or by the action of a thermal polymerization initiator described later by heating. It is a compound having an ethylenic double bond that cures. In addition, the monomer in this invention means the concept which opposes what is called a polymeric substance, and means the concept also containing a dimer, a trimer, and an oligomer other than the monomer of a narrow sense.

Examples of the ethylenic compound include an unsaturated carboxylic acid, an ester thereof with a monohydroxy compound, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, An ester obtained by an esterification reaction with a saturated carboxylic acid and a polyvalent carboxylic acid and a polyvalent hydroxy compound such as the above-mentioned aliphatic polyhydroxy compound or aromatic polyhydroxy compound;
Examples thereof include an ethylenic compound having a urethane skeleton obtained by reacting a (meth) acryloyl-containing hydroxy compound.

  Examples of esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propane triacrylate, trimethylol ethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate. And acrylic esters such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate. In addition, the acrylic acid part of these acrylates is a methacrylic acid ester replaced with a methacrylic acid part, an itaconic acid ester replaced with an itaconic acid part, a crotonic acid ester replaced with a crotonic acid part, or a maleic acid replaced with a maleic acid part Examples include esters.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance but may be a mixture. Typical examples include, for example, condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, butanediol. And condensates of glycerin and the like.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; cyclohexane diisocyanate and isophorone diisocyanate. Alicyclic diisocyanates; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 3-hydroxy (1,1,1-triacryloyloxymethyl) propane, 3- (Meth) acryloyl group-containing hydroxy compounds such as hydroxy (1,1,1-trimethacryloyloxymethyl) propane Reaction products thereof.

In addition, as the ethylenic compound, for example, acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate are also useful.
The ethylenic compound may be a monomer having an acid group. The monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound is reacted with a non-aromatic carboxylic acid anhydride to form an acid group. A polyfunctional monomer is preferred, and in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used alone, but since it is difficult to use a single compound in production, two or more kinds may be used in combination. Moreover, you may use together the polyfunctional monomer which does not have an acid group as a monomer, and the polyfunctional monomer which has an acid group as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polyfunctional monomer is too low, the development and dissolution properties are lowered, and if it is too high, the production and handling are difficult, the photopolymerization performance is lowered, and the curability such as the surface smoothness of the pixel tends to be poor. Accordingly, when two or more polyfunctional monomers having different acid groups are used in combination, or when a polyfunctional monomer having no acid group is used in combination, the acid groups as the entire polyfunctional monomer should be adjusted so as to fall within the above range. Is preferred.

  More preferred polyfunctional monomers having acid groups are dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and dipentaerythritol pentaacrylate succinic acid ester, which are commercially available as TO1382 manufactured by Toagosei Co., Ltd. It is. Other polyfunctional monomers can be used in combination with this polyfunctional monomer.

  (F) The blending ratio of the polymerizable monomer is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, and usually 80% by weight in the total solid content of the colored resin composition of the present invention. % Or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. The ratio to the colorant is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less, preferably 100% by weight. Hereinafter, it is more preferably 80% by weight or less.

<(G) Photopolymerization initiators and / or thermal polymerization initiators>
The colored resin composition of the present invention preferably further comprises (g) photopolymerization initiators and / or thermal polymerization initiators for the purpose of curing the coating film. However, the curing method may be other than those using these initiators.
In particular, when the colored resin composition of the present invention includes (c) a resin having an ethylenic double bond as a binder resin component, or (f) when an ethylenic compound is included as the polymerizable monomer component described above, Photopolymerization initiators that have the function of directly absorbing light or being photosensitized to cause decomposition reaction or hydrogen abstraction reaction to generate polymerization active radicals, and / or thermal polymerization initiation that generates polymerization active radicals by heat It is preferable to contain agents.

In the present invention, the component (g) as a photopolymerization initiator is a photopolymerization initiator (hereinafter sometimes referred to as (g-1) component) or a polymerization accelerator (hereinafter referred to as (g-2). ), A sensitizing dye (hereinafter, sometimes referred to as (g-3) component), and the like.
<Photopolymerization initiators>
The (g) photopolymerization initiators that may be contained in the colored resin composition of the present invention are usually (g-1) a photopolymerization initiator and, if necessary, added (g-3). Used as a mixture with an additive such as a dye-sensitive dye and (g-2) a polymerization accelerator, and directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical It is a component having

  (G) Photopolymerization initiators (g-1) Examples of photopolymerization initiators include titanocene derivatives described in JP-A Nos. 59-152396 and 61-151197; Hexaarylbiimidazole derivatives described in JP-A-10-300922, JP-A-11-174224, JP-A-2000-56118, etc .; Halomethylated oxadiazoles described in JP-A-10-39503 Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, radical activators such as N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; oxime ester derivatives described in JP 2000-80068 A and the like .

Specifically, for example, titanocene derivatives include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro Phen-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluorophen-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny 1-yl), dicyclopentadienyl titanium di (2,6-difluorophen-1-yl), dicyclopentadienyl titanium di (2,4-difluorophen-1-yl), di (methylcyclopenta Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclone) Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-difluoro-3- (pyro-1-yl) -phen-1-yl] and the like. Can be mentioned.

  As biimidazole derivatives, 2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole 2 amount 2- (2′-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) ) -4,5-diphenylimidazole dimer and the like.

  The halomethylated oxadiazole derivatives include 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl). Vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2- And trichloromethyl-5-furyl-1,3,4-oxadiazole.

  Examples of halomethyl-s-triazine derivatives include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl). ) -S-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s -Triazine etc. are mentioned.

Examples of the α-aminoalkylphenone derivatives include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) ) Coumarin, 4- (diethylamino) chalcone, etc. The

The oxime ester derivatives include 1,2-octanedione, 1- [4- (phenylthio) phenyl], 2- (o-benzoyloxime), ethanone, 1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl], 1- (o-acetyloxime) and the like.
In addition, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- ( acetophenone derivatives such as p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone are also included.

Among these (g-1) photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, and thioxanthone derivatives are more preferable.
Moreover, the colored resin composition of this invention can mix | blend (g-2) a polymerization accelerator further as needed, especially when (g) photoinitiators are included. (G-2) Examples of the polymerization accelerator include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these (g-1) photopolymerization initiator and (g-2) polymerization accelerator may be used alone or in combination of two or more.
In the colored resin composition of the present invention, (g-3) a sensitizing dye may be used in the photopolymerization initiators for the purpose of increasing the sensitivity. (G-3) As the sensitizing dye, an appropriate dye is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc. A coumarin dye having a heterocyclic ring described in JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin described in JP-A-3-239703, JP-A-5-289335, etc. Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, JP 57-168088, JP No. 5-107761, JP-A-5-210240, it may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP-A 4-288818 Patent JP-like.

Among these (g-3) sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. (G-3) Particularly preferred as a sensitizing dye is, for example, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4′-diaminobenzophenone. Benzophenone compounds such as 3,3′-diaminobenzophenone and 3,4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethyl) Aminophenyl) benzo [4,5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-oxazole, 2- (p-dimethylaminophenyl) benzothiazo 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1 , 3,4-thiadiazole, (p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) pyrimidine, P-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl) pyrimidine. Of these, 4,4'-dialkylaminobenzophenone such as 4,4'-dimethylaminobenzophenone and 4,4'-diethylaminobenzophenone is most preferred.

(G-3) A sensitizing dye may also be used individually by 1 type, and may use 2 or more types together.
In the colored resin composition of the present invention, the content of these (g) photopolymerization initiators ((g-1) photopolymerization initiator, (g-2) polymerization accelerator and (g-3) sensitizing dye) The ratio is usually 0.1% by weight or more, preferably 0.5% by weight or more, and usually 40% by weight or less, preferably 30% by weight or less in the total solid content.

<Thermal polymerization initiators>
Specific examples of the thermal polymerization initiators that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used.
Examples of the azo compound include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexene-1-carbonitrile), 2, 2′-azobis (2,4-dimethylvaleronitrile), 1-[(1-cyano-1-methylethyl) azo] formamide (2- (carbamoylazo) isobutyronitrile), 2,2-azobis {2 -Methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2′-azobis [N- (2-propenyl) -2-methylpropionamide], 2,2 '-Azobis [N- (2-propenyl) -2-ethylpropionamide], 2,2'-azobis [N-butyl-2-methylpropionamide], 2,2'-azobis (N-cyclo Xyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionamide), 2,2′-azobis (dimethyl-2-methylpropionate), 2,2′-azobis (2 , 4,4-trimethylpentene) and the like. Among these, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) and the like are preferable. .

Examples of the organic peroxide include benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide and the like. Specifically, diisobutyryl peroxide, cumylperoxyneodecanoate, di-n-propylperoxydicarbonate, diisopropylperoxydicarbonate, di-sec-butylperoxydicarbonate, 1,1,3, 3-tetramethylbutylperoxyneodecanoate, di (4-t-butylcyclohexyl) peroxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di (2-ethoxyethyl) peroxy Dicarbonate, di (2-ethylhexyl) peroxydicarbonate, t-hexylperoxyneodecanoate, dimethoxybutylperoxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t -Butyl peroxypivale Di (3,5,5-trimethylhexanoyl) peroxide, di-n-octanoyl peroxide, dilauroyl peroxide, distearoyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2 -Ethylhexanoate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, t-butylperoxy-2-ethylhexanoate, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (T-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy)
Cyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane, t-hexylperoxyisopropyl monocarbonate, t- Butyl peroxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (3-methylbenzoylperoxy) Hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butyl peroxyacetate, 2,2-di (t-butylperoxy) butane, -Butyl peroxybenzoate, n-butyl-4,4-di (t-butylperoxy) valerate, di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butyl) Peroxy) hexyne-3, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, t-butyltrimethylsilyl peroxide, 2,3 -Dimethyl-2,3-diphenylbutane, di (3-methylbenzoyl) peroxy Mixtures of benzoyl (3-methylbenzoyl) peroxide and dibenzoyl peroxide may be mentioned.

In addition, some of the above-described (g-1) photopolymerization initiators also function as thermal polymerization initiators such as α-aminoalkylphenone derivatives. Therefore, you may use the compound selected from the examples given as an example of (g-1) photoinitiator as a thermal-polymerization initiator.
These thermal polymerization initiators may be used individually by 1 type, and may use 2 or more types together.
When the ratio of the thermal polymerization initiators in the colored resin composition is too small, the film is not sufficiently cured and the durability as a color filter may be insufficient. If the amount is too large, the degree of thermal shrinkage increases, and cracking and cracking may occur after thermosetting. Moreover, the tendency for storage stability to fall is seen. Therefore, the content of the thermal polymerization initiators is preferably in the range of 0 to 30% by weight, particularly 0 to 20% by weight, based on the total solid content of the colored resin composition of the present invention.

<Surfactant>
The colored resin composition of the present invention may further contain a surfactant. Various surfactants such as anionic, cationic, nonionic, and amphoteric surfactants can be used as surfactants, but they may adversely affect various properties such as voltage holding ratio and compatibility with organic solvents. It is preferable to use a nonionic surfactant in terms of low properties.

  Examples of anionic surfactants include alkyl sulfate ester surfactants such as “Emar 10” manufactured by Kao Corporation, and alkylnaphthalene sulfonate surfactants such as “Perex NB-L” manufactured by Kao Corporation. And special polymer surfactants such as “Homogenol L-18” and “Homogenol L-100” manufactured by Kao Corporation. Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

  Examples of the cationic surfactant include alkylamine salt surfactants such as “Acetamine 24” manufactured by Kao Corporation, and quaternary ammonium salt interfaces such as “Cotamine 24P” and “Coatamine 86W” manufactured by Kao Corporation. Examples include activators. Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred.

Nonionic surfactants include, for example, “SH8400” manufactured by Tore Silicone; silicone surfactants such as “KP341” manufactured by Silicone; “FC430” manufactured by Sumitomo 3M; Dainippon Ink and Chemicals, Inc. "F470" manufactured by KK; fluorine-based surfactants such as "DFX-18" manufactured by Neos; polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation, etc. . Of these, silicone surfactants are preferable, and so-called polyether-modified or aralkyl-modified silicone surfactants having a structure in which a side chain of a polyether group or an aralkyl group is added to polydimethylsiloxane are more preferable.

Two or more surfactants may be used in combination, for example, silicone surfactant / fluorine surfactant, silicone surfactant / special polymer surfactant, fluorine surfactant / special polymer. And combinations of surfactants. Of these, a combination of silicone surfactant / fluorine surfactant is preferable.
Examples of the silicone surfactant / fluorine surfactant combination include a polyether-modified silicone surfactant / oligomer-type fluorine surfactant combination. Specifically, for example, “TSF4460” manufactured by GE Toshiba Silicone Co., Ltd. “DFX-18” manufactured by Neos Co., Ltd., “BYK-300” manufactured by Big Chemie Co., Ltd., “S-393” manufactured by Seimi Chemical Co., Ltd., “KP340 manufactured by Shin-Etsu Silicone Co., Ltd. "F-478" manufactured by Dainippon Ink & Chemicals, "SH7PA" manufactured by Tore Silicone, "DS-401" manufactured by Daikin, "L-77" manufactured by Nihon Unicar, and "FC4430" manufactured by Sumitomo 3M The combination of is mentioned.

  The content of these surfactants is usually 0.001% by weight or more, preferably 0.005% by weight or more, and more preferably 0.01% by weight or more in the total solid content. Further, it is usually used in the range of 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less. By controlling the surfactant content within this range, there is no possibility that the overcoat will be repelled when the overcoat is applied in the actual line, and the coating film may be cracked after curing. The film is less likely to wrinkle.

<Thermal polymerization inhibitor>
As the thermal polymerization inhibitor, for example, hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t-butyl-p-cresol, β-naphthol and the like are used. The blending amount of the thermal polymerization inhibitor is preferably in the range of 0% by weight to 3% by weight with respect to the total solid content of the composition.

<Plasticizer>
Examples of the plasticizer include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. The blending amount of these plasticizers is preferably in the range of usually 10% by weight or less with respect to the total solid content of the composition.

<Preparation method of colored resin composition>
Next, a method for preparing the colored resin composition of the present invention will be described.
First, (a) the coloring material according to the present invention is composed of (b) a solvent which is an essential component, and (c) a binder resin, and in some cases, an optional component (f) a polymerizable monomer or (g) photopolymerization. A colored resin composition is obtained by mixing with initiators and / or thermal polymerization initiators, surfactants, and other components to form a uniform solution. In mixing, it is preferable to stir until (a) the coloring material is sufficiently dissolved. In addition, since fine dust may be mixed in each step such as mixing, it is preferable to filter the obtained ink-like liquid with a filter or the like.

When (d) the pigment is used in combination as the color material, first, (a) the color material, (d) the pigment, (b) the solvent and the optional component (e) the dispersant according to the present invention, In addition, in the dispersion treatment step, (d) the pigment is sufficiently dispersed to obtain an ink-like liquid. In this dispersion treatment step, a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like can be used. By performing this dispersion treatment, (d) the pigment is made into fine particles, so that the coating characteristics of the colored resin composition are improved, and the transmittance of the product color filter substrate and the like is improved.

  (D) When the pigment is subjected to a dispersion treatment, it is preferable to use a part of the (c) binder resin as a dispersant or to appropriately use a dispersion aid or the like. Moreover, when performing a dispersion process using a paint shaker or a sand grinder, it is preferable to use glass beads or zirconia beads having a diameter of 0.1 to several mm. The temperature during the dispersion treatment is usually set to 0 ° C. or higher, preferably room temperature or higher, and usually 100 ° C. or lower, preferably 80 ° C. or lower. The dispersion time needs to be appropriately adjusted because the appropriate time varies depending on the composition of the ink-like liquid and the size of the sand grinder apparatus.

  In addition to the ink-like liquid obtained by the above dispersion treatment, (c) a binder resin, which is an essential component, and (b) a solvent, and in some cases, an optional component (f) a polymerizable monomer or (g) initiation of photopolymerization. The colored resin composition is obtained by mixing the agents, and / or the thermal polymerization initiator, the surfactant, and other components to obtain a uniform dispersion solution. In addition, in each process of a dispersion | distribution process and mixing, since fine refuse may mix, it is preferable to filter the obtained ink-like liquid with a filter etc.

<Application of colored resin composition>
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter, a liquid crystal display device (panel) and an organic EL display using them will be described.

<Color filter pixels>
The pixel of the color filter can be formed by various methods as will be described later. Here, the case of forming by photolithographic method using a photopolymerizable colored resin composition will be described in detail, but the manufacturing method is not limited to this.
The material of the transparent substrate of the color filter is not particularly limited as long as it is transparent and has an appropriate strength. Examples of the material include polyester resins such as polyethylene terephthalate; polyolefin resins such as polypropylene and polyethylene; polycarbonate resins; acrylic resins such as polymethyl methacrylate; sheets made of thermoplastic resins such as polysulfone resins; Examples thereof include thermosetting resin sheets such as unsaturated polyester resins; and various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. For these transparent substrates, surface treatment such as corona discharge treatment or ozone treatment, thin film formation treatment with various resins such as silane coupling agents or urethane resins, etc. Etc. may be performed. The thickness of the transparent substrate is usually 0.05 mm or more, preferably 0.1 mm or more, and usually 10 mm or less, preferably 7 mm or less. Moreover, when performing the thin film formation process by various resin, the film thickness is 0.01 micrometer or more normally, Preferably it is 0.05 micrometer or more, and is 10 micrometers or less normally, Preferably it is the range of 5 micrometers or less.

A color filter can be produced by providing a black matrix on the above-described transparent substrate and further forming each pixel image of red, green and blue.
The black matrix uses a light-shielding metal thin film or the colored resin composition of the present invention,
It is formed on a transparent substrate.
As the light-shielding metal material, a chromium compound such as metal chromium, chromium oxide, chromium nitride, an alloy of nickel and tungsten, or the like may be used, and these may be laminated in a plurality of layers. These light shielding metal thin films are generally formed by a sputtering method, and a desired pattern is formed in a film shape by a positive photoresist.

  For chromium, an etchant mixed with ceric ammonium nitrate and perchloric acid and / or nitric acid is used. For other materials, etching is performed using an etchant according to the material, and finally positive. A black matrix can be formed by stripping the mold photoresist with a dedicated stripper. In this case, first, a thin film of these metals or metal / metal oxide is formed on the transparent substrate by vapor deposition or sputtering. Next, a coating film of a positive photoresist resin composition is formed on the thin film. Next, the coating film is exposed and developed using a photomask having a repetitive pattern such as a stripe, a mosaic, and a triangle to form an image. Thereafter, this coating film can be etched to form a black matrix.

  Moreover, you may form a black matrix using the photopolymerizable coloring resin composition containing a black (d) pigment. For example, black obtained by mixing black pigments such as carbon black, graphite, iron black, titanium black, etc., alone or in combination, or pigments such as red, green, blue, etc., appropriately selected from inorganic or organic pigments Using a colored resin composition containing a pigment, a black matrix can be formed in a manner similar to the method of forming red, green, and blue pixel images described later.

  For the black colored resin composition, on the transparent substrate, for the red, green, and blue colored resin compositions, use the resin black matrix forming surface formed on the transparent substrate, or a chromium compound or other light shielding metal material. A pixel image of each color is formed on the metal black matrix forming surface formed in this way through the processes of coating, heat drying, image exposure, development and thermosetting.

  On a transparent substrate provided with a black matrix, a colored resin composition containing a color material of one of red, green, and blue is applied and dried, and then a photomask is overlaid on the coating film. Then, a pixel image is formed by image exposure, development, and if necessary, heat curing or photocuring to create a colored layer. A color filter image can be formed by performing this operation for each of the three colored resin compositions of red, green, and blue.

Here, the colored resin composition of the present invention is particularly preferably used for forming a blue pixel.
As a method for supplying the colored resin composition to the substrate, there are conventionally known methods such as a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method and the like. Can be mentioned. Among these, the slit and spin method and the die coating method are preferable. Since the colored resin composition of the present invention hardly generates agglomerated foreign matter at the tip of the dispensing nozzle, it is possible to provide a coating film having a smooth and beautiful surface without reducing the yield. In addition, there is no coating unevenness during the coating or drying unevenness in the subsequent drying step, and a layer having an extremely smooth surface can be formed through an exposure step, a development step, a heat treatment step, and the like.

The coating conditions by the slit-and-spin method and the die coating method may be appropriately selected depending on the composition of the colored resin composition, the type of color filter to be produced, and the like. For example, in both methods, the lip width at the nozzle tip is preferably 50 to 500 μm, and the distance between the nozzle tip and the substrate surface is preferably 30 to 300 μm.
In the die coating method, in order to adjust the thickness of the coating film, the running speed of the lip and the discharge amount of the liquid colored resin composition from the lip may be adjusted. In the slit and spin method, Further, it may be adjusted depending on the spin rotation speed and the rotation time after slit coating.

  If the coating film is too thick, pattern development becomes difficult and gap adjustment in the liquid crystal cell forming process may be difficult. On the other hand, if the coating film is too thin, it is difficult to increase the pigment concentration. Color expression may be impossible. The thickness of the coating film is usually 0.2 μm or more, preferably 0.5 μm or more, more preferably 0.8 μm or more, and usually 20 μm or less, preferably 10 μm or less, more preferably 5 μm as the film thickness after drying. The range is as follows.

The coating film after the colored resin composition is applied to the substrate is preferably dried by a drying method using a hot plate, an IR oven, or a convection oven. Usually, after preliminary drying, it is heated again and dried.
Conditions such as predrying temperature and drying time are appropriately selected according to the type of solvent component, the performance of the dryer used, and the like. Specifically, the drying temperature is usually 40 ° C. or higher, preferably 50 ° C. The drying time is usually 15 ° C. or less, preferably 70 ° C. or less, and the drying time is usually 15 seconds or more, preferably 30 seconds or more, and usually 5 minutes or less, preferably 3 minutes or less.

  The reheating drying temperature condition is preferably higher than the pre-drying temperature. Specifically, it is usually 50 ° C. or higher, preferably 70 ° C. or higher, and usually 200 ° C. or lower, preferably 160 ° C. or lower, particularly preferably. Is in the range of 130 ° C. or lower. The drying time depends on the heating temperature, but it is usually 10 seconds or longer, preferably 15 seconds or longer, and usually 10 minutes or shorter, preferably 5 minutes or shorter. The higher the drying temperature, the better the adhesion to the transparent substrate. However, when the drying temperature is too high, the binder resin is decomposed, and thermal polymerization may be induced to cause development failure. In addition, as a drying process of this coating film, you may use the reduced pressure drying method which dries in a reduced pressure chamber, without raising temperature.

  Image exposure is performed by superimposing a negative matrix pattern on the coating film of the colored resin composition and irradiating a UV or visible light source through this mask pattern. At this time, if necessary, exposure is performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer in order to prevent a decrease in sensitivity due to oxygen of the photopolymerizable layer formed of the colored resin composition. May be.

  The light source used for said image exposure is not specifically limited. Examples of the light source include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, fluorescent lamps, and the like; argon ion lasers, YAG lasers, excimers Laser light sources such as laser, nitrogen laser, helium cadmium laser, and semiconductor laser are listed. An optical filter can also be used when used by irradiating light of a specific wavelength.

The color filter is a substrate obtained by performing image exposure on the coating film of the colored resin composition with the above light source and then developing with an organic solvent or an aqueous solution containing a surfactant and an alkaline compound. An image can be formed on the top. This aqueous solution may further contain an organic solvent, a buffering agent, a complexing agent, a dye or a pigment.
Here, as the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-di- or tri-ethanolamine, mono-di- or tri-methylamine , Mono-di- or tri-ethylamine, mono-or diisopropylamine, n-butylamine, mono-di-or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide ( TMAH The organic alkaline compound of choline, and the like. These alkaline compounds may be used individually by 1 type, and may use 2 or more types together.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters; and alkylbenzene sulfonic acids. Anionic surfactants such as salts, alkylnaphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkyl betaines and amino acids. These surfactants may be used alone or in combination of two or more.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. An organic solvent may be used individually by 1 type, may be used as a 2 or more types of mixed solvent, and can also be used in combination with aqueous solution.
There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred.

The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.
The color filter after development is subjected to heat curing. In this case, the thermosetting treatment conditions are such that the temperature is usually 100 ° C. or higher, preferably 150 ° C. or higher, and usually 280 ° C. or lower, preferably 250 ° C. or lower. Selected by range.

Through these series of steps, the patterning image formation for one color is completed. This process is sequentially repeated to pattern black (when forming a black matrix using a colored resin composition), red, green, and blue to form a color filter. Note that the patterning order of the three colors red, green, and blue is not limited to the order described above.
In addition to the above-described manufacturing method, the color filter according to the present invention is a pixel image formed by applying (1) a colored resin composition containing a polyimide resin as a solvent, a coloring material, and a binder resin to a substrate. It can also be produced by a method of forming Also, (2) a method of forming a pixel image directly on a transparent substrate by using a colored resin composition containing a color material as a color ink, and (3) an electrodeposition solution containing the color resin composition containing the color material A method of depositing a colored film on an ITO electrode having a predetermined pattern by immersing the substrate in this electrodeposition solution, and (4) a film coated with a colored resin composition containing a coloring material, A method of forming a pixel image by attaching and peeling to a substrate, image exposure and development, (5) A method of forming a pixel image on a substrate by an ink jet printer using a colored resin composition containing a coloring material as a coloring ink, etc. Can also be produced. As a method for producing the color filter, a method suitable for this is employed according to the composition of the colored resin composition of the present invention.

When the color filter thus produced is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image as it is and used as a part of a component such as a color display or a liquid crystal display device. Although used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image as necessary. Further, in some applications such as a planar alignment type drive system (IPS mode), the transparent electrode may not be formed. In the vertical alignment type driving method (MVA mode), ribs may be formed. Also, a column structure (photo spacer) made of photolithography may be formed instead of the bead dispersion type spacer.

<Liquid crystal display device (panel)>
The liquid crystal display device according to the present invention includes the above-described color filter (hereinafter sometimes referred to as “the color filter of the present invention”). For example, the above-described color filter of the present invention and a thin film transistor (TFT). It can comprise by making it the structure which opposes opposing board | substrates etc. through the liquid-crystal layer. More specifically, an alignment film is formed on the color filter of the present invention, spacers are dispersed on the alignment film, and then bonded to each other through a counter substrate and a peripheral sealing material to form a liquid crystal cell. It is manufactured by injecting liquid crystal into a liquid crystal cell and connecting to a counter electrode.

  The alignment film is preferably a resin film such as polyimide. Gravure printing and / or flexographic printing methods are usually used to form the alignment film. After coating, the alignment film is cured by thermal baking, and then subjected to surface treatment by ultraviolet irradiation or rubbing cloth treatment. Then, it is processed into a surface state in which the tilt of the liquid crystal can be adjusted. The thickness of the alignment film thus formed is usually about several tens of nm.

A spacer having a size corresponding to a gap (gap) with the counter substrate is used, and usually a spacer having a size of 2 to 8 μm is preferable. A photo spacer (PS) of a transparent resin film can be formed on the color filter by photolithography, and this can be used instead of the spacer.
As the counter substrate, an array substrate is usually used, and a TFT (thin film transistor) substrate is particularly preferable. Moreover, although the gap of bonding with a counter substrate changes with uses of a liquid crystal panel, it is normally selected in the range of 2 micrometers or more and 8 micrometers or less.

After the color filter is bonded to the counter substrate, portions other than the liquid crystal injection port are sealed with a sealing material such as an epoxy resin. The sealing material is cured by ultraviolet (UV) irradiation and / or heating, and the periphery of the liquid crystal cell is sealed.
The liquid crystal cell whose periphery is sealed is cut into panel units, then decompressed in a vacuum chamber, the liquid crystal injection port is immersed in liquid crystal, and then the liquid crystal is injected into the liquid crystal cell by leaking in the chamber. . In this case, the degree of decompression in the liquid crystal cell is usually 1 × 10 ⁻² Pa or higher, preferably 1 × 10 ⁻³ Pa or higher, and usually 1 × 10 ⁻⁷ Pa or lower, preferably 1 × 10 ⁻⁶ Pa or lower. It is a range. The liquid crystal cell is preferably heated during decompression, and the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and usually 100 ° C. or lower, preferably 90 ° C. or lower. The warming holding time during decompression is usually in the range of 10 minutes or more and 60 minutes or less, and then immersed in the liquid crystal.

In the liquid crystal cell into which liquid crystal is injected, a liquid crystal display device is completed by sealing the liquid crystal injection port by, for example, curing a UV curable resin.
The type of liquid crystal to be used is not particularly limited, and any conventionally known liquid crystal such as an aromatic, aliphatic or polycyclic compound may be used, such as a lyotropic liquid crystal or a thermotropic liquid crystal. As the thermotropic liquid crystal, nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like are known, and any of these may be used.

<Organic EL display>
When producing an organic EL display comprising the color filter of the present invention, for example, as shown in FIG. 3, a blue color filter in which blue pixels 20 are formed on the transparent support substrate 10 by the colored resin composition of the present invention. A multicolor organic EL element can be produced by laminating the organic light-emitting body 500 via the organic protective layer 30 and the inorganic oxide film 40 thereon. As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display and an active drive type organic EL display.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In addition, this invention is not limited to description of a following example, unless the summary is exceeded.
<Examples 1-17 and Comparative Examples 1-5>
[1] Synthesis of dye
Synthesis Example 1 Synthesis of Intermediate BP1

Reaction 1: Thionyl chloride (14 ml, 200 mmol) was added to a mixture of Compound 1 (25 g, 129 mmol) and toluene (100 ml), stirred at 80 ° C. for 1 hour, and then concentrated under reduced pressure to obtain acid chloride. In a separate container, a mixture of anhydrous aluminum chloride (20.4 g, 155 mmol) and 1,2-dichloroethane (100 ml) was cooled in an ice bath, and a solution of acid chloride in 1,2-dichloroethane (50 ml) was added dropwise. After stirring for 15 minutes, Compound 2 (21.1 g, 129 mmol) was added dropwise to room temperature, and then poured into ice water. The pH was adjusted to 10 or more with 4N aqueous sodium hydroxide solution, and the mixture was extracted with chloroform. The chloroform layer was washed with 1N aqueous sodium hydroxide solution and filtered through Celite to remove insolubles. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The product was purified by silica gel column chromatography (silica gel 800 g, hexane / ethyl acetate 4/1), and the obtained crystals were washed with hexane to obtain BP1 (14.6 g, yield 33%).

  Synthesis Example 2 Synthesis of Intermediate BP2

Reaction 2: A mixture of compound 3 (10.8 g, 50 mmol), thionyl chloride (5.3 ml, 75 mmol), chloroform (10 ml) and N, N-dimethylformamide (1 drop) was heated to reflux for 2 hours, and then at atmospheric pressure. Concentration gave the acid chloride. In a separate container, aluminum chloride (7.91 g, 60 ml) and 1,2-dichloroethane (40 ml) were taken, cooled in an ice bath, and a 1,2-dichloroethane (20 ml) solution of acid chloride was added dropwise. After stirring for 15 minutes, compound 2 (
8.16 g, 50 mmol) of 1,2-dichloroethane (10 ml) was added dropwise. After stirring at room temperature for a while, it was poured into ice water. The pH was adjusted to 10 or more with 4N aqueous sodium hydroxide solution, and the mixture was extracted twice with chloroform. The chloroform layer was washed with 1N aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (silica gel 500 g, hexane / ethyl acetate 15 / 1-10 / 1) gave compound 4 (7.25 g, yield 40%).

Reaction 3: Compound 4 (7.25 g, 20.1 mmol), diethylamine (4.14 ml, 40 mmol), sodium-t-butoxide (2.31 g, 24 mmol), palladium acetate (0.045 g, 0.2 mmol), tri A mixture of -t-butylphosphine (10% hexane solution, 1.6 ml, 0.8 mmol) and toluene (100 ml) was stirred at 80-100 ° C. for 5 hours. Diethylamine (4.14 ml, 40 mmol) was added during the reaction. After cooling to room temperature, ice water was added for liquid separation, and the organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. Concentrate under reduced pressure and purify by silica gel column chromatography (silica gel 300 g, hexane / ethyl acetate 7 / 1-5 / 1).
P2 (2.92 g, 41% yield) was obtained.

  Synthesis Example 3 Synthesis of Intermediate BP3

Reaction 4: BP3 was synthesized in the same manner as in Reaction 1 using Compound 1 and Compound 5.
Synthesis Example 4 Synthesis of Intermediate BP4

Reaction 5: A mixture of m-toluidine (Compound 6) (18.6 g, 174 mmol), isobutyl iodide (50 ml, 434 mmol), potassium carbonate (60 g, 435 mmol), N-methyl-2-pyrrolidone (200 ml) The mixture was stirred for 3 hours at 140 ° C. and 14 hours at 140 ° C. After cooling to room temperature, it was diluted with toluene (400 ml), filtered with suction, and washed with toluene (100 ml). Water was added to the filtrate and the toluene layer was separated and washed four times with water. The toluene layer was concentrated under reduced pressure and purified by silica gel column chromatography (silica gel 800 g, hexane / ethyl acetate 100 / 0-100 / 1-50 / 1-30 / 1) to give compound 7 (24.4 g, yield 64). %).

Reaction 6: Aluminum chloride (8.75 g, 65.6 mmol) and 1,2-dichloroethane
A mixture of (10 ml) was cooled in an ice bath and a solution of compound 8 (12.0 g, 54.7 mmol) in 1,2-dichloroethane (20 ml) was added dropwise over 15 minutes. The mixture was stirred for 20 minutes, and then a solution of compound 7 (12.0 g, 54.7 mmol) in 1,2-dichloroethane (20 ml) was added dropwise over 10 minutes and stirred as it was for 1 hour. Stirring was continued for about 2.5 hours while raising the temperature to room temperature. It was poured into ice water and washed with chloroform. The pH was adjusted to 10 or higher with 4N aqueous sodium hydroxide solution, and the mixture was extracted with chloroform. The chloroform layer was washed with 1N aqueous sodium hydroxide solution three times and dried over anhydrous sodium sulfate. Concentration under reduced pressure and purification by silica gel column chromatography (hexane / ethyl acetate 15 / 1-10 / 1) gave compound 9 (8.85 g, yield 40%) as a yellow powder.

Reaction 7: Compound 9 (8.5 g, 21.1 mmol) and toluene (100 ml) were mixed with diisobutylamine (7.3 ml, 42.2 mmol), sodium t-butoxy (4.06 g, 42.2 mmol), acetic acid. Palladium (II) (284 mg, 1.27 mmol), tri-t-butylphosphine (10% hexane solution, 552 mg, 2.53 mmol)
) And heated to reflux for 5.5 hours. After cooling to room temperature, a small amount of water was added, filtered through Celite, washed with toluene, and the filtrate was extracted with toluene. The toluene layer was washed 3 times with saturated brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, silica gel column chromatography (hexane / ethyl acetate 15 / 1-10 / 1) compound BP4 (8.3 g, yield 88%) was obtained as a yellow oil.

  Synthesis Example 5 Synthesis of Intermediate BP5

Reaction 8: Compound 6 (2.56 g, 23.9 mmol), 1,1,1-trifluoro-4-iodobutane (TCI, 12.5 g, 52.5 mmol), potassium carbonate (7.25 g, 52.5 mmol) And N-methyl-2-pyrrolidone (50 ml) was stirred at 100 ° C. for 5 hours, then cooled to room temperature, diluted with ethyl acetate, filtered with suction, and washed with ethyl acetate. The mother liquor was washed twice with water and then concentrated under reduced pressure. The oil was dissolved in toluene, washed 3 times with water, and washed with saturated brine. It was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica gel column chromatography (Kanto Chemical 60N, 200 g, hexane / ethyl acetate 20 / 1-15 / 1) to give compound 10 (6.91 g, yield 88%). Got.

Reaction 9: BP5 was obtained in the same manner as in Reaction 1, using Compound 1 and Compound 10.
Synthesis Example 6 Synthesis of Intermediate BP6

Reaction 10: Compound 11 (4.06 g, 30 mmol), 1,1,1-trifluoro-4-iodobutane (7.85 g, 33 mmol), potassium carbonate (4.55 g, 33 mmol), N-methyl-2-pyrrolidone The mixture (50 ml) was stirred at 100 ° C. for 7 hours, poured into water, extracted with toluene, and the toluene layer was washed 5 times with water and saturated brine. The extract was dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain Compound 12 (7.44 g).

Reaction 11: BP6 was obtained in the same manner as in Reaction 1, using Compound 1 and Compound 11.
Synthesis Example 7 Synthesis of Intermediate BP7

Reaction 12: Compound 13 was obtained in the same manner as in Reaction 6 using Compound 8 and Compound 10.
Reaction 13: BP7 was obtained in the same manner as in Reaction 7 using Compound 13.
Synthesis Example 8 Synthesis of Intermediate NA1

Reaction 14: Mixture of compound 14 (14.3 g, 100 mmol), 2-ethylhexyl bromide (19.2 g, 100 mmol), potassium carbonate (15.2 g, 110 mmol), N-methyl-2-pyrrolidone (100 ml) at 120 ° C. And stirred at 140 ° C. for 2 hours. After cooling to room temperature, toluene was added and suction filtered, and toluene and water were added to the mother liquor to separate the toluene layer. The toluene layer was washed 4 times with water and then concentrated under reduced pressure. Purification by column chromatography (silica gel 300 g, hexane / ethyl acetate 100 / 1-50 / 1-30 / 1) gave NA1 (8.88 g, yield 37%).

  Synthesis Example 9 Synthesis of Intermediate NA2

Reaction 15: NA2 was obtained in the same manner as in Reaction 14, using Compound 14 and isobutyl iodide.
Synthesis Example 10 Synthesis of Intermediate NA3

Reaction 16: Compound 15 (6.0 g, 25 mmol), 1,1,1-trifluoro-4-iodobutane (6.4 ml, 50 mmol), potassium carbonate (6.9 g, 50 mmol), N-methyl-2-pyrrolidone (25 ml) of the mixture was heated and stirred at 110 to 125 ° C. for 4 hours. Extraction was performed with toluene, and the toluene layer was washed with 1N aqueous hydrochloric acid solution, further washed with saturated brine, and dried over anhydrous sodium sulfate. Concentration under reduced pressure gave 9.2 g of a light brown oil. It melt | dissolved in ethanol (40 ml), the water (25 ml) solution of sodium hydroxide (2g, 52.3 mmol) was added there, and it heated and stirred at 85 degreeC for 1 hour. The mixture was allowed to cool, extracted with toluene, washed with saturated brine, and dried over anhydrous sodium sulfate. The solution was concentrated under reduced pressure and purified by silica gel column chromatography (hexane / ethyl acetate 3/1) to obtain NA3 (5.95 g, yield 94%) as a white powder.

  Synthesis Example 11 Synthesis of D1

Reaction 17: Phosphorus oxychloride (1.4 ml, 15 mmol) was added to a mixture of BP1 (3.38 g, 10 mmol), NA4 (1.71 g, 10 mmol) and toluene (15 ml), and the mixture was stirred at 120 ° C. for 2 hr. After cooling to room temperature, 1N hydrochloric acid was added, stirred for 15 minutes, and extracted with chloroform. The chloroform layer was washed with water and saturated brine, and dried over anhydrous sodium sulfate. After concentration under reduced pressure and purification by silica gel column chromatography (chloroform / methanol 15 / 1-10 / 1-7 / 1), the resulting solid was washed with hexane to give C1 (3.21 g,
Yield 61%).

Reaction 18: C1 (1.06 g, 2.0 mmol) and acid blue 80 (0.70 g, 1.03 mmol) were dissolved in methanol and concentrated under reduced pressure. The obtained solid was washed with a mixed solvent of methanol / water (1/2) to obtain D1 (1.34 g, yield 83%).
(Synthesis example 12) Synthesis | combination of D2 D2 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP2 instead of BP1.

(Synthesis example 13) The synthesis | combination of D3 D3 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP3 instead of BP1.
(Synthesis example 14) Synthesis | combination of D4 D4 was obtained by operation similar to the reaction 17 and the reaction 18 except having used NA1 instead of NA4.

(Synthesis example 15) Synthesis | combination of D5 D5 was obtained by operation similar to the reaction 17 and the reaction 18 except having used NA2 instead of NA4.
(Synthesis example 16) Synthesis | combination of D6 D6 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP4 instead of BP1, and NA2 instead of NA4.

(Synthesis Example 17) Synthesis of D7 BP4 was used instead of BP1, NA1 was used instead of NA4, and D7 was obtained in the same manner as in Reaction 17 and Reaction 18 except that.
(Synthesis example 18) Synthesis | combination of D8 D8 was obtained by operation similar to reaction 17 and reaction 18 except having used BP5 instead of BP1.

(Synthesis example 19) The synthesis | combination of D9 D9 was obtained by operation similar to the reaction 17 and the reaction 18 except having used (±) sodium camphorsulfonate instead of acid blue 80.
(Synthesis example 20) Synthesis | combination of D10 D10 was obtained by operation similar to the reaction 17 and the reaction 18 except having used NA3 instead of NA4.

(Synthesis example 21) Synthesis | combination of D11 D11 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP5 instead of BP1, and using NA3 instead of NA4.
(Synthesis example 22) The synthesis | combination of D12 D12 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP5 instead of BP1, and NA2 instead of NA4.

(Synthesis example 23) The synthesis | combination of D13 D13 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP4 instead of BP1 and NA3 instead of NA4.
(Synthesis example 24) The synthesis | combination of D14 D14 was obtained by operation similar to the reaction 17 and the reaction 18 except having used BP6 instead of BP1, and NA2 instead of NA4.

(Synthesis example 25) Synthesis | combination of D15 D15 was obtained by operation similar to reaction 17 and reaction 18 except having used BP7 instead of BP1.
(Synthesis example 26) Synthesis | combination of D16 D17 was obtained by operation similar to reaction 17 and reaction 18 except having used BP5 instead of BP1, and using acid green 25 instead of acid blue 80.

(Synthesis example 27) Synthesis | combination of D17 D17 was obtained by operation similar to reaction 17 and reaction 18 except having used BP5 instead of BP1, and using sodium naphthalene-1-sulfonate instead of acid blue 80.
(Synthesis Example 28) Synthesis of D18 (hereinafter sometimes referred to as “target XB”)

  11.5 g of 1-aminonaphthalene was dissolved in 120 g of N-methyl-2-pyrrolidone, and 3.74 g of sodium amide was added with stirring at room temperature. Further, after adding 1.20 g of sodium iodide as a catalyst and 0.89 g of 2,5-di-t-butylhydroquinone as a polymerization inhibitor, 13.4 g of p-chloromethylstyrene was added over 30 minutes, and at room temperature. Stir for 2 hours. After stirring, 200 ml of chloroform was added and dissolved, followed by washing with water three times. The chloroform layer was separated and the solvent was distilled off to obtain a residue. This was purified by silica gel column chromatography to obtain 10.8 g of p-vinylbenzylnaphthylamine as an intermediate.

  10.8 g of the obtained intermediate, 17.6 g of 4,4′-bis (diethylamino) benzophenone, 0.46 g of 2,5-di-tert-butylhydroquinone as a polymerization inhibitor and 140 g of toluene were added as solvents, and a nitrogen atmosphere The mixture was heated to 45 ° C., and 8.31 g of phosphorus oxychloride was added over 10 minutes. After completion of dropping, the temperature was raised to 100 ° C. over 1 hour and stirred at 100 ° C. for 1 hour. After completion of stirring, the mixture was cooled to room temperature, and toluene was distilled off under reduced pressure. 200 ml of chloroform was added and dissolved therein, followed by washing with water three times. The chloroform layer was separated and the solvent was distilled off to obtain a residue, which was purified by silica gel column chromatography to obtain the desired product X-B (5.9 g).

[2] Synthesis of Binder Resin (Synthesis Example 29) Synthesis of Binder Resin a 145 parts by weight of propylene glycol monomethyl ether acetate was stirred while being replaced with nitrogen, and the temperature was raised to 120 ° C. 20 parts by weight of styrene, 57 parts by weight of glycidyl methacrylate and 82 parts by weight of monoacrylate having a tricyclodecane skeleton (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) were added dropwise thereto, and the mixture was further stirred at 120 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 0.7 parts by weight of trisdimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were added to 27 parts by weight of acrylic acid, and the reaction was continued at 120 ° C. for 6 hours. Then, 52 parts by weight of tetrahydrophthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were added and reacted at 120 ° C. for 3.5 hours. The weight average molecular weight Mw measured by GPC of the binder resin a thus obtained was about 15000. The structure of the binder resin a was as shown below (polymer compound containing the following four types of repeating units).

(Synthesis Example 30) Synthesis of Binder Resin b 35 parts of propylene glycol monomethyl ether acetate, 8.8 parts of 1-methoxy-2-propanol, V-59 (azo-based polymerization initiator manufactured by Wako Pure Chemical Industries, Ltd.) 1.5 Parts were charged in a reaction vessel, heated to 80 ° C. in a nitrogen atmosphere, 18.0 parts of benzyl methacrylate and 12.0 parts of methacrylic acid were added dropwise over 2 hours, and further stirred for 4 hours. Obtained. Further, 25.5 parts of propylene glycol monomethyl ether acetate was added to this polymerization reaction solution, 0.05 parts of p-methoxyphenol and 0.3 parts of triphenylphosphine were added and dissolved, and then (3,4-epoxycyclohexyl). ) 13.5 parts of methyl acrylate was added dropwise and reacted at 85 ° C. for 24 hours to obtain a resin solution having an ethylenically unsaturated group in the side chain. The thus obtained binder resin had a polymerization average molecular weight by GPC of 18000 in terms of polystyrene, and neutralization titration with KOH. The acid value was 90. The structure of the binder resin b was as shown below (polymer compound containing the following three types of repeating units).

[3] Preparation of colored resin composition [3-1] Preparation of dye-based composition (Examples 1 to 17 and Comparative Examples 1 to 5)
Table 1 shows the dyes (pigments) used in Examples 1 to 17 and Comparative Examples 1 to 4.

  The above dyes and other components were mixed at the ratios shown in Table 2 to prepare a colored composition. In mixing, the mixture was stirred for 1 hour or more until the dye was sufficiently dissolved, and finally filtered through a 5 μm piece filter to remove foreign matters.

[3-2] Preparation of pigment-based composition (Comparative Example 5)
As a pigment, C.I. I. Pigment Blue 15: 6 and 11.29 parts by weight of C.I. I. Pigment Violet 23 is 0.61 part by weight, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are mixed in a ratio of 7: 3 as 80.16 parts by weight, and polymer dispersant Disperbyk2000 manufactured by BYK Chemie is used as a dispersant. (Acrylic block copolymer. AB block copolymer consisting of a B block having a quaternary ammonium base (dimethylbenzylammonium base) and an A block having no quaternary ammonium base, and an amine value of 10 mg KOH / g (solid content conversion) The acid value is 0 mg KOH / g) 3.97 parts by weight in terms of solids, and the binder resin b (obtained in Synthesis Example 30) as a dispersion resin is 3.97 parts by weight in terms of solids, with a diameter of 0. 250.0 parts by weight of 5mm zirconia beads in stainless steel It was filled in, to prepare a blue pigment dispersion for 6 hours and dispersed by a paint shaker.

  The pigment dispersion thus obtained and other components were mixed at the ratios shown in Table 3 to prepare a colored composition. During mixing, the mixture was stirred for 1 hour or more until the pigment dispersion and other components were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.

[4] Spectral characteristics and heat / light resistance evaluation
Each colored resin composition is applied onto a glass substrate cut into 5 cm square by spin coating so as to have a dry film thickness of 1.8 μm, dried under reduced pressure, and then prebaked at 80 ° C. for 3 minutes on a hot plate. did. Thereafter, the entire surface was exposed with an exposure amount of 60 mJ / cm ² , and then the spectral transmittance was measured with a spectrophotometer U-3310 manufactured by Hitachi, Ltd., and the chromaticity (C light source) in the XYZ color system was calculated. The results are summarized in Table 4.

Next, the substrate is placed between two polarizing plates in close contact with no gap, and a light intensity A (cd / cd) when the polarizing plates are orthogonal using a color luminance meter ("BM-5A" manufactured by Topcon). from the ratio of cm ²⁾ and the light amount at the time of parallel B (cd / cm ^2), and calculates the contrast C by the following equation (1). These results are summarized in Table 4.
C = B / A (1)
Subsequently, after the substrate was baked at 230 ° C. for 30 minutes in the clean oven, the spectral transmittance was measured as described above, and the color difference (ΔE * ab) from the chromaticity before baking, that is, the heat resistance was measured. Are summarized in Table 4.

As shown in Table 4, the color filter formed using the colored resin composition for a color filter of the present invention has a high contrast ratio and excellent heat resistance.
Next, chromaticity measurement was performed by combining the coated substrate with an organic electroluminescent (EL) element.
[5] Preparation of organic electroluminescent device
The organic electroluminescence device shown in FIG. 2 was produced by the following method.

An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 having a thickness of 150 nm (sputtered film; sheet resistance 15Ω) is patterned into a 2 mm wide stripe using ordinary photolithography and hydrochloric acid etching. Thus, an anode 2 was formed. The patterned ITO substrate was cleaned in the order of ultrasonic cleaning with acetone, water with pure water, and ultrasonic cleaning with isopropyl alcohol, dried with nitrogen blow, and finally subjected to ultraviolet ozone cleaning. Subsequently, 9,9-bis [4- (N, N-bisnaphthylamino) phenyl] -9H-fluorene (LT-N121, manufactured by Luminescent Technology) represented by the formula IX is used as the hole transport layer 3 in a crucible temperature 285. The film was laminated at a film thickness of 40 nm at a vapor deposition rate of 0.1 nm / sec at a temperature of from 310 ° C. The degree of vacuum at the time of vapor deposition was 1.7 × 10 ⁻⁴ Pa.

  Next, as the light-emitting layer 4, 2,2′-diperylenyl-9,9′-spirobifluorene (LT-N428, manufactured by Luminescent Technology) represented by the formula X and 2,7-bis [9,9 represented by the formula XI are used. '-Spirobifluorenyl] -9,9'-spirobifluorene (LT-N628, manufactured by Luminescent Technology) was co-evaporated under the following conditions.

(Light-emitting layer deposition conditions)
LT-N428 crucible temperature 320 ° C-330 ° C
LT-N628 crucible temperature 450 ° C-455 ° C
Deposition rate of LT-N428 0.1 nm / sec
Deposition rate of LT-N628 0.05 nm / second
Under the above conditions, the films were stacked with a film thickness of 30 nm. The degree of vacuum at the time of deposition was 1.7 to 1.9 × 10 ⁻⁴ Pa. Subsequently, 1,3-bis [2- (2,2′-bipyridinyl) -1,3,4-oxadiazoyl] -benzene (LT-N820) represented by Formula XII as the electron transport layer 5 is formed on the light-emitting layer 4. , Manufactured by Luminescent Technology) with a film thickness of 30 nm. At this time, the crucible temperature of LT-N820 is controlled in the range of 255 ° C. to 260 ° C., the deposition rate is controlled in the range of 0.08 nm / second to 0.1 nm / second, and the degree of vacuum during the deposition is 1.2 × 10 ⁻⁴ Pa. Met.

In addition, the substrate temperature at the time of vacuum-depositing said positive hole transport layer 3, the light emitting layer 4, and the electron carrying layer 5 was kept at room temperature. Here, the element formed up to the electron transport layer 5 was once taken out from the vacuum deposition apparatus into the atmosphere. Next, a stripe shadow mask having a width of 2 mm was brought into close contact with the element so as to be orthogonal to the ITO stripe of the anode 2 as a mask for cathode vapor deposition. Subsequently, this element was placed in another vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the vacuum vapor deposition apparatus was 2.3 × 10 ⁻⁵ Pa or less, as in the case where the organic layer was formed. Next, as the cathode 9, first, lithium fluoride (LiF) was deposited using a molybdenum boat at a deposition rate of 0.008 nm / second to 0.01 nm / second at a vacuum degree of 3.7 × 10 ⁻⁶ Pa. The film was formed on the electron transport layer 5 with a film thickness of 5 nm. Subsequently, similarly, the aluminum was heated by a molybdenum boat, the film thickness at a deposition rate of 0.1 nm / sec to 0.2 nm / sec, the vacuum degree ^{2.7 × 10 -6 Pa~2.5 × 10 -6} Pa A cathode 6 was completed by forming an aluminum layer of 80 nm. When forming the above two-layer cathode 6, the substrate temperature during vapor deposition was kept at room temperature. As described above, an organic electroluminescent device having a light emitting area portion having a size of 2 mm × 2 mm was prepared.

The presence or absence of light emission and the color of light emitted when a voltage of 6 V was applied to the device were evaluated. The maximum wavelength of the EL emission spectrum at this time was 436 nm, and the CIE chromaticity coordinates (CIE chromaticity coordinates when the front luminance was 10 to 1000 cd / m ² ) were (0.16, 0.15).
[6] Spectral characteristics evaluation The chromaticity was measured by combining the organic electroluminescent light emitting device and the coated substrates of Examples 1 to 17 and Comparative Examples 1 to 5. The results are summarized in Table 5.

  Further, regarding the evaluation of heat resistance, the same tendency as the result in the case of using the C light source is shown.

1, 10 Transparent support substrate 2, 50 Transparent anode 3, 52 Hole transport layer 4, 53 Light emitting layer 5, Electron transport layer 6, 55 Cathode 100 Organic EL element 20 Blue color filter 30 Organic protective layer 40 Inorganic oxide film 500 Organic light emission Body 51 hole injection layer 54 electron injection layer

Claims (13)

(A) a coloring material, (b) a solvent, and (c) a binder resin,
(A) A colored resin composition for a color filter, wherein the color material contains a compound represented by the following general formula (I).

(In the general formula (I), [Z] ^m− represents an arbitrary m-valent anion.
R ^{1 to} R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. When R ^{1 to} R ⁶ represent an alkyl group which may have a substituent, adjacent R ¹ and R ² , R ³ and R ⁴ , or R ⁵ and R ⁶ are bonded to form a ring structure. It may be.
X represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may have a substituent.
Y each independently represents a hydrogen atom or an arbitrary substituent (excluding the same substituent as X) .
In addition, multiple molecules in one molecule

May be the same structure or different structures.
m represents an arbitrary natural number. )   In the said general formula (I), Y is a hydrogen atom, The coloring resin composition for color filters of Claim 1 characterized by the above-mentioned. The colored resin composition for a color filter according to claim 1 or 2 , wherein the compound represented by the general formula (I) is a compound represented by the general formula (i).

(R ^{1 to} R ⁶ , X, Y, [Z] ^m− , m in the general formula (i) are the same as those in the general formula (I).) The colored resin composition for a color filter according to any one of claims 1 to 3 , wherein the X is a methyl group. The colored resin composition for a color filter according to any one of claims 1 to 4 , wherein at least one of the R ^{1 to} R ⁶ is a fluorine atom-containing group. Wherein [Z] ^m-is, the color filter for the colored resin composition according to any one of claims 1 to 5, characterized in that a sulfonic acid anion. The colored resin composition for a color filter according to any one of claims 1 to 6 , wherein the compound represented by the general formula (I) is a compound represented by the general formula (v).

(In the said general formula (v), m, Y, and R < ¹ > -R < ⁵ > are synonymous with those in the general formula (I).
R ³¹ represents a hydrogen atom or an optionally substituted phenyl group;
R ^{32 to} R ³⁴ each independently represent a hydrogen atom, a hydroxyl group, —NHR ⁴¹ (R ⁴¹ has the same meaning as R ³¹ ), —SO ₃ ⁻ , a halogen atom, —CO ₂ R ⁴² (R ⁴² represents carbon. Represents an alkyl group of 1 to 3), and at least one of R ^{32 to} R ³⁴ is a —NHR ⁴¹ group.
R ^{35 to} R ³⁸ are each independently a hydrogen atom, —SO ₃ ⁻ , a halogen atom, a phenoxy group, a naphthyloxy group, an alkoxyl group having 1 to 12 carbon atoms, —CO ₂ R ⁴³ , a phenyl group, —SO ₃ R ⁴⁴ or —SO ₂ NHR ⁴⁵ (wherein R ^{43 to} R ⁴⁵ each independently represents an alkyl group having 1 to 6 carbon atoms).
Further, m —SO ₃ ^— groups are bonded to one anthraquinone skeleton.
In addition, when two or more cation frame | skeleton specified in the said general formula (v) is contained in 1 molecule, they may be the same structure or a different structure. ) The color according to any one of claims 1 to 7 , wherein the content of the compound represented by the general formula (I) is 5% by weight or more based on the total amount of the color material (a). Colored resin composition for filters. The colored resin composition for a color filter according to any one of claims 1 to 8 , further comprising (f) a polymerizable monomer. The colored resin composition for a color filter according to any one of claims 1 to 9 , further comprising (g) a photopolymerization initiator and / or a thermal polymerization initiator. Color filter and having a pixel fabricated using the claim 1 color resin composition for color filters of any one of 10. A liquid crystal display device comprising the color filter according to claim 11 . An organic EL display comprising the color filter according to claim 11 .

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