JP7063023B2 - Colored resin composition, color filter and image display device - Google Patents

Description

The present invention resides in a colored resin composition, a color filter and an image display device.

Flat panel displays such as liquid crystal displays and organic EL (Electroluminescence) display devices are widely used, and color filters are used in these displays. In keeping with the trend of energy saving, color filters are required to have higher color purity, higher brightness and higher contrast.
So far, a colored resin composition using a pigment has been mainly used as a material for forming a color filter. However, in order to obtain high brightness and high contrast, for example, in Non-Patent Document 1, the particle size of the pigment particles is set. A method of finely dispersing the color to less than 1/2 of the color-developing wavelength is disclosed.

On the other hand, dyes are also being developed as coloring materials used in colored resin compositions for color filters. For example, Patent Document 1 discloses a colored resin composition for a color filter containing a specific coloring material and a blue coloring material.

Japanese Unexamined Patent Publication No. 2014-153570

Kiyoshi Hashizume, "Journal of the Japan Society of Color Material", December 1967, p608

Conventionally, among red, green, and blue, the transmittance peak of the blue pixel is relatively low, and it is necessary to improve the overall brightness while maintaining the balance at the time of white display. Therefore, among the pixels of the color filter. Vigorous studies have been conducted on the dyeing of blue pixels. On the other hand, in recent years, there has been a trend toward higher brightness from the viewpoint of power consumption, and therefore there is a demand for dyeing the red pixels of color filters.
As a result of the study by the present inventors, it is necessary to have a high transmittance in the vicinity of 560 to 650 nm in the red pixel application of the color filter, so that it is sufficiently dissolved in a solvent in order to increase the brightness. It was found that it was necessary to use dyes.
The colored resin composition described in Patent Document 1 is intended for use in blue pixels, and no studies have been made on applications for red pixels. Further, as a result of the study by the present inventors, it has been found that the dye described in Patent Document 1 has insufficient luminance in practical use in red pixel applications.

Therefore, the present invention has been made in view of the above-mentioned problems of the prior art, and an object of the present invention is to provide a colored resin composition containing a dye sufficiently soluble in a solvent and having excellent brightness.

As a result of diligent studies by the present inventors, they have found that the above problems can be solved by using a novel xanthene dye having a specific structure, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] A colored resin composition containing (A) a coloring material, (B) a solvent, and (C) a binder resin.
A colored resin composition, wherein the coloring material (A) contains a xanthene dye represented by the following general formula (I).

(In the above formula (I), R ¹ to R ⁶ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k independently represent an integer of 0 to 5, and l and m each independently represent an integer of 0 to 3.
X ¹ and X ² each represent an alkylene group which may independently have a substituent, and one or more of the methylene groups constituting the alkylene group are -O-, -S-, -CO-, and-. It is replaced by at least one selected from the group consisting of NR ⁷ −. However, the number of atoms constituting the main chain of X ¹ and X ² is 4 or more. )

[2] The colored resin composition according to [2], wherein the coloring material (A) further contains a red pigment.
[3] The colored resin composition according to [1] or [2], which further contains (D) a polymerizable monomer.
[4] The colored resin composition according to any one of [1] to [3], further containing (E) a photopolymerization initiation component and / or (E') a thermal polymerization initiation component.
[5] The colored resin composition according to any one of [1] to [4], further containing an antioxidant.

[6] A color filter having pixels formed by using the colored resin composition according to any one of [1] to [5].
[7] An image display device having the color filter according to [6].

According to the present invention, it is possible to provide a colored resin composition containing a dye sufficiently soluble in a solvent and having excellent brightness.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL device having the color filter of the present invention. FIG. 2 is a transmission spectrum of the polarizing plate used for evaluating the light resistance of the examples.

Hereinafter, embodiments of the present invention will be described in detail, but the following description is an example of embodiments of the present invention, and the present invention is not limited to these contents.
In the present invention, "(meth) acrylic", "(meth) acrylate" and the like mean "at least one of acrylic and methacrylic", "at least one of acrylate and methacrylate" and the like, for example, "( "Meta) Acrylic acid" shall mean "at least one of acrylic acid and methacrylic acid".

Further, the "total solid content" means all the components of the colored resin composition of the present invention other than the solvent component.
Further, the "aromatic ring" shall mean both an "aromatic hydrocarbon ring" and an "aromatic heterocycle".
In addition, terms such as "CI pigment green" mean the names of color materials contained in the Color Index (CI).

The colored resin composition of the present invention contains (A) a coloring material, (B) a solvent and (C) a binder resin, and the (A) coloring material is a xanthene-based material represented by the general formula (I) described later. It is characterized by containing a dye. Further, it is preferable to contain at least one of (D) a polymerizable monomer, and (E) a photopolymerization initiating component and (E') a thermal polymerization initiating component, and may contain other components as necessary. ..

[(A) Color material]
(Xanthene dye represented by the general formula (I))
The (A) coloring material contained in the colored resin composition of the present invention contains a xanthene dye represented by the following general formula (I) (hereinafter, may be referred to as "xanthene dye (I)"). do.

In the above formula (I), R ¹ to R ⁶ independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k independently represent an integer of 0 to 5, and l and m each independently represent an integer of 0 to 3.
X ¹ and X ² each represent an alkylene group which may independently have a substituent, and one or more of the methylene groups constituting the alkylene group are -O-, -S-, -CO-, and-. It is replaced by at least one selected from the group consisting of NR ⁷ −. However, the number of atoms constituting the main chain of X ¹ and X ² is 4 or more.

As described above, the xanthene dye (I) has four or more atoms constituting the main chain of X ¹ and X ² , which facilitates twisting and rotational movement of the bond, and also X ¹ It is considered that the methylene group constituting the alkylene group in X ² is replaced with the polar group, so that the affinity with the solvent becomes higher and the solubility becomes higher. As a result, the transmittance at 560 to 650 nm is high, the transmittance at less than 560 nm is low, a rectangular transmission spectrum is obtained, and it is considered that the brightness in red pixel applications is very high.
On the other hand, since the number of atoms constituting the main chain of X ¹ and X ² is 4 or more, the twisting and rotational motion of the bond becomes easy, and even if it is photoexcited, it does not radiate due to internal conversion and vibrational relaxation. It is easily deactivated and is thought to improve light resistance. Furthermore, it is considered that the benzene ring bonded to X ¹ and X ² facilitates stacking due to π-π interaction and hydrophobic interaction between molecules, and easily causes deactivation of the excited state to improve light resistance.

(X ¹ and X ² )
In the formula (I), X ¹ and X ² each represent an alkylene group which may independently have a substituent, and one or more of the methylene groups constituting the alkylene group are —O—, —S—. , -CO-, and -NR ^7- are replaced by at least one selected from the group. However, the number of atoms constituting the main chain of X ¹ and X ² is 4 or more.

Examples of the alkylene group in X ¹ and X ² include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded, and the alkylene group is linear from the viewpoint of easiness of synthesis. The alkylene group of is preferred.
The number of carbon atoms of the alkylene group is usually preferably 4 or more, 5 or more, preferably 15 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 7 or less. When it is at least the lower limit value, the solubility tends to be improved, and when it is at least the upper limit value, synthesis tends to be easy.

Specific examples of the alkylene group include a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group and the like, and a pentylene group is preferable from the viewpoint of solubility and easiness of synthesis.

One or more of the methylene groups constituting the alkylene groups of X ¹ and X ² are replaced by at least one selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- . In this case, the number of substitutions may be 1 or 2 or more. That is, one or more of the methylene groups constituting the alkylene group may be replaced with one selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- , and the alkylene group may be replaced. One or more of the constituent methylene groups may be replaced by two or more combinations selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- . Examples of the combination of two or more types include -O-CO-, -CO-O-, and -CO-NR ⁷ .

Further, any of the methylene groups constituting the alkylene group may be replaced with the above-mentioned group, but from the viewpoint of easiness of synthesis, the methylene group adjacent to the benzene ring in the formula (I) is replaced with the above-mentioned group. It is preferable to replace it.
The number of atoms constituting the main chain of X ¹ and X ² is 4 or more, preferably 5 or more, preferably 15 or less, more preferably 12 or less, further preferably 10 or less, and particularly preferably 7 or less. When it is at least the lower limit value, the solubility tends to be improved, and when it is at least the upper limit value, synthesis tends to be easy.

As X ¹ and X ² , divalent groups represented by the following general formula (I-1) are preferable from the viewpoint of ease of synthesis.

In formula (I-1), X ³ represents an alkylene group having 3 or more carbon atoms. X ⁴ represents at least one selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- . * ¹ represents a bond with an adjacent N atom, and * ² represents a bond with an adjacent benzene ring.

(X ³ )
In the formula (I-1), X ³ represents an alkylene group having 3 or more carbon atoms. Examples of the alkylene group include a linear alkylene group, a branched chain alkylene group, a cyclic alkylene group, and a group in which these are bonded, and a linear alkylene group is preferable from the viewpoint of solubility.
The number of carbon atoms of the alkylene group is usually 3 or more, 4 or more, more preferably 5 or more, more preferably 14 or less, further preferably 11 or less, further preferably 9 or less, still more preferably 7 or less. The following are particularly preferred. When it is at least the above lower limit value, the solubility tends to be further improved, and when it is at least the above upper limit value, synthesis tends to be easy.

Specific examples of the alkylene group include a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group and the like, and a butylene group is preferable from the viewpoint of ease of synthesis.

(X ⁴ )
In the formula (I-1), X ⁴ represents at least one selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- . It may be one kind selected from the group consisting of -O-, -S-, -CO-, and -NR ^7- , or a combination of two or more kinds. Examples of the combination of two or more types include -O-CO-, -CO-O-, and -CO-NR ⁷ .

Among these, from the viewpoint of solubility, -O-CO-, -CO-O-, -O-, and -CO- are preferable, and -O-CO- or -O- are more preferable.

(R ¹ to R ⁶ )
In the formula (I), R ¹ to R ⁶ independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.

Examples of the alkyl group in R ¹ to R ⁶ include a linear, branched or cyclic alkyl group. The carbon number thereof is preferably 1 or more, more preferably 2 or more, further preferably 3 or more, particularly preferably 4 or more, preferably 10 or less, more preferably 6 or less, still more preferably 5 or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at most the upper limit value, synthesis is easy, crystallization is easy, and purification is easy.

Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylethyl group and 3-. Examples thereof include a methylbutyl group. Among these, a methyl group, an ethyl group and an n-propyl group are preferable from the viewpoint of easiness of synthesis.

Examples of the alkoxy group in R ¹ to R ⁶ include a linear, branched or cyclic alkoxy group. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, more preferably 10 or less, still more preferably 6 or less, still more preferably 4 or less. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at most the upper limit value, synthesis is easy, crystallization is easy, and purification is easy.

Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butyloxy group, 2-propyloxy group, isobutyloxy group, tert-butyloxy group, cyclohexyloxy group, cyclohexylmethyloxy group and cyclohexylethyl. Examples thereof include an oxy group and a 3-methylbutyloxy group. Among these, a methoxy group and an ethoxy group are preferable from the viewpoint of crystallinity and ease of purification.

Examples of the halogen atom in R ¹ to R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable, and a chlorine atom is more preferable, from the viewpoint of ease of synthesis and solubility.

Among these, as R ¹ and R ² , from the viewpoint of easiness of synthesis and crystallinity, an alkyl group and a halogen atom which may have a substituent are preferable, and a halogen atom is more preferable.

On the other hand, among these, as R ³ and R ⁴ , alkyl groups which may have a substituent are preferable from the viewpoint of heat resistance and color tone.

Among these, as R ⁵ and R ⁶ , alkyl groups which may have a substituent are preferable from the viewpoint of heat resistance.

(H to k)
In the formula (I), h to k each independently represent an integer of 0 to 5.
h and i are each independently preferably 1 or more, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less. When it is at least the lower limit value, the solubility tends to be improved, and when it is at least the upper limit value, synthesis tends to be easy.
When h and i are 1 or more, the substitution position is not particularly limited, but the 2-position and 4-position are preferable, and the 4-position is more preferable.

On the other hand, j and k are each independently preferably 1 or more, more preferably 2 or more, preferably 4 or less, and more preferably 3 or less. When the wavelength is equal to or higher than the lower limit, the wavelength of the absorption peak tends to be longer, and when the molar absorption coefficient is higher, the brightness tends to be improved. There is a tendency to suppress the decrease in brightness due to.
When j and k are 1 or more, the substitution position is not particularly limited, but the 2nd, 4th, and 6th positions are preferable, and the 2nd and 6th positions are more preferable.

(L and m)
In the above formula (I), l and m each independently represent an integer of 0 to 3.
From the viewpoint of heat resistance, l and m are preferably 0 to 2 independently, and more preferably 0 to 1.
On the other hand, from the viewpoint of ease of synthesis, l and m are preferably 0.

When l and m are 1 or more, the substitution position is not particularly limited, but when the position adjacent to the nitrogen atom is the 1st position and the 2nd position is the clockwise adjacent part, the 2nd and 6th positions are. The second position is preferable, and the second position is more preferable.

Examples of the substituents that the alkyl group and the alkoxy group in R ¹ to R ⁶ and the alkylene group in X ¹ and X ² may have include those of the following substituent group W1.

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group with 2 to 8 carbon atoms, alkoxyl group with 1 to 8 carbon atoms, phenyl group, mesityl group, trill group, naphthyl group, cyano group, acetyloxy group, alkyl with 2 to 9 carbon atoms A carbonyloxy group, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, an alkylcarbonyl group having 2 to 9 carbon atoms, a phenethyl group, a hydroxyethyl group, an acetylamide group, and an alkyl group having 1 to 4 carbon atoms are bonded. A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms.
Among them, an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkylcarboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom are preferable. ..

Further, the present form of the xanthene dye represented by the above formula (I) in the colored resin composition is not particularly limited, but it is preferably present in a form dissolved in a solvent from the viewpoint of luminance and contrast.

(Molecular weight)
The molecular weight of the xanthene dye represented by the general formula (I) is not particularly limited, but is preferably 600 or more, more preferably 700 or more, further preferably 750 or more, particularly preferably 800 or more, and preferably 1500 or less. 1400 or less is more preferable, 1300 or less is further preferable, and 1250 or less is particularly preferable. When it is at least the lower limit value, the heat resistance tends to be improved, and when it is at least the upper limit value, synthesis tends to be easy.

(Specific example of xanthene dye represented by formula (I))
Specific examples of the xanthene dye represented by the formula (I) include the following.

(Method for synthesizing xanthene dye represented by formula (I))
The xanthene dye of the present invention can also be synthesized by using a commercially available xanthene dye (for example, "DCSF" manufactured by Chugai Kasei Co., Ltd.) as a starting material and referring to JP2013-253168A.

(Content ratio of xanthene dye represented by formula (I))
The coloring material (A) in the colored resin composition of the present invention may contain one kind of xanthene dye represented by the formula (I), or may contain two or more kinds.
The content ratio of the coloring material (A) in the colored resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and 30% by mass or more in the total solid content. Is even more preferable, 35% by mass or more is particularly preferable, 38% by mass or more is most preferable, 80% by mass or less is preferable, 70% by mass or less is more preferable, 60% by mass or less is further preferable, and 50% by mass or less. Is particularly preferable. When it is at least the above lower limit value, it tends to be easy to obtain desired color characteristics, and when it is at least the above upper limit value, there is a tendency that the photosensitivity is improved.

The content ratio of the xanthene dye represented by the formula (I) in the (A) coloring material is not particularly limited, but is preferably 5% by mass or more, preferably 10% by mass or more, based on the (A) coloring material. More preferably, 20% by mass or more is further preferable, 25% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 40% by mass or less is particularly preferable. preferable. When it is at least the lower limit value, the brightness tends to be improved, and when it is at least the upper limit value, the durability tends to be good.

(Other color materials)
The coloring material (A) in the colored resin composition of the present invention may contain other coloring materials in addition to the xanthene dye represented by the general formula (I). Examples of other coloring materials include other dyes and pigments.
The content ratio of the other coloring materials is not particularly limited, but is preferably 1% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, still more preferably 20% by mass or more, based on the total solid content. 25% by mass or more is particularly preferable, 70% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, and 40% by mass or less is particularly preferable. Further, the content ratio of other coloring materials in (A) coloring material is not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. It is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less. When it is at least the above lower limit value, durability and color characteristics tend to be compatible, and when it is at least the above upper limit value, the photosensitivity tends to be improved.

(Other dyes)
Examples of other dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, and triarylmethane dyes. Dipyrromethene dyes, xanthene dyes and the like are preferably mentioned.

Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Moldant Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples include Moldant Black 7.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 25, C.I. I. Acid Blue 40, C.I. I. Acid Blue 80, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse blue 60 and the like can be mentioned.

In addition, as a phthalocyanine dye, for example, C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Batblue 5, JP-A-2002-14222, JP-A-2005-134759, JP-A-2010-191358, JP-A-2011-148950 and the like can be used as quinoneimine dyes, for example, C. .. I. Basic Blue 3, C.I. I. Basic blue 9 and the like are used as quinoline dyes, for example, C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like can be used as nitro dyes, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like can be mentioned.

Further, as the triarylmethane dye, for example, C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Examples thereof include those described in Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, and the like.
Further, examples of the cyanine-based dye include those described in International Publication No. 2011/162217, and preferred embodiments are also the same.

Examples of the dipyrromethene dye include JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A. Examples thereof include those described in JP-A-2012-158739, JP-A-2012-224852, JP-A-2012-224489, JP-A-2012-224847, JP-A-2012-224846, and the like.

Examples of the xanthene dye include C.I. I. Acid Red 50, C.I. I. Acid Red 52, C.I. I. Acid Red 289, Japanese Patent No. 3387541, Japanese Patent Application Laid-Open No. 2010-32999, Japanese Patent No. 4492760, "Review Synthetic Dyes" (Horiguchi Hiroshi, Sankyo Publishing, 1968), pp. 326-348, etc. Can be mentioned.
In particular, when forming red pixels, xanthene dyes are preferable from the viewpoint of luminance and heat resistance.
The colored resin composition of the present invention may contain only one type of other dye, or may contain two or more types.

(Pigment)
As the pigment, for example, when forming red pixels of a color filter or the like, pigments of various colors such as red and yellow can be used.
Examples of the chemical structure of the pigment include organic pigments such as phthalocyanine-based, quinacridone-based, benzimidazolone-based, dioxazine-based, indanthrone-based, and perylene-based. In addition to this, various inorganic pigments and the like can also be used. Hereinafter, specific examples of pigments that can be used are shown by pigment numbers.

Examples of the red pigment include 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, 179, 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. Among these, from the viewpoint of brightness, C.I. I. Pigment Red 177, 254, or 275, more preferably C.I. I. Pigment Red 177 or 254. Further, from the viewpoint of contrast, it is preferable to use the diketopyrrolopyrrole pigment represented by the formula (P) described in JP2013-014750. One of these may be used alone, or two or more thereof may be mixed and used in any combination and ratio.

Examples of the yellow pigment 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, 173, 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 and the like can be mentioned. Among these, from the viewpoint of brightness, C.I. I. Pigment Yellow 129, 138, 139, 150 or 185, more preferably C.I. I. Pigment Yellow 138, 150 or 185.
One of these may be used alone, or two or more thereof may be mixed and used in any combination and ratio.

The pigment that can be used in the colored resin composition of the present invention preferably has a small average primary particle size from the viewpoint of forming pixels with high contrast, and specifically, the average primary particle size is 40 nm or less. Is preferable, and it is more preferably 35 nm or less.
Here, the average primary particle size of the pigment can be a value measured and calculated by the following method.

First, the pigment is ultrasonically dispersed in chloroform, dropped onto a collodion film-attached mesh, dried, and observed with a transmission electron microscope (TEM) to obtain a primary particle image of the pigment. From this image, the particle size of each of a plurality of (usually about 200 to 300) pigment particles is determined as the diameter equivalent to an area circle converted into the diameter of a circle having the same area.
Using the obtained primary particle size value, calculate the number average value according to the formula below to obtain the average particle size.

Particle size of individual pigment particles: X ₁ , X ₂ , X ₃ , X ₄ , ..., X _i , ... X _m (m is the number of particles)

Among other coloring materials, it is preferable to contain other pigments from the viewpoint of improving heat resistance and light resistance. In particular, when forming red pixels, it is preferable to contain a red pigment from the viewpoint of chromaticity, luminance and contrast, and C.I. I. Pigment Red 177, C.I. I. Pigment Red 254, a diketopyrrolopyrrole pigment represented by the formula (P) described in JP2013-014750 is more preferable.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of dissolving or dispersing each component contained in the colored resin composition and adjusting the viscosity.
The solvent (B) may be any solvent as long as it can dissolve or disperse each component constituting the colored resin composition, and it is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120 to 170 ° C.

Examples of such a solvent include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol-monot-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene Glycol monoalkyl ethers such as glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol monomethyl ether;

Glycoldialkyl 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;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monoethyl Glycolalkyl ether acetates such as ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3-methoxybutyl acetate;

Ethers such as diethyl ether, dipropyl ether, diisopropyl ether, diamil ether, ethylisobutyl ether, dihexyl ether;
Ketones such as 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;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amilformate, ethylformate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methylisobutyrate, ethylene glycol acetate, ethylpropionate, propylpropionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Chain or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amilk chloride;
Etheretones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

It is preferable to contain glycol monoalkyl ethers in the solvent from the viewpoints of adhesion between the substrate and the coating film and the ability to form a uniform film thickness of the coating film. Of these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various constituents in the colored resin composition.
Further, for example, when the above-mentioned other pigment is contained as an optional component, the balance of coatability, surface tension and the like is good, and the solubility of the component in the colored resin composition is relatively high, so that the glycol is further used as a solvent. It is more preferable to use a mixture of alkyl ether acetates. In the colored resin composition containing a pigment, glycol monoalkyl ethers have high polarity and tend to aggregate the pigment, which may reduce the storage stability such as increasing the viscosity of the colored resin composition. Therefore, it is preferable that the amount of the glycol monoalkyl ethers used is not excessively large, and the ratio of the glycol monoalkyl ethers in the solvent (B) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass. ..

Further, from the viewpoint of suitability for the slit coating method corresponding to recent large substrates and the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher in combination. In this case, the content of such a high boiling point solvent is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 5 to 30% by mass with respect to the whole solvent (B). If the amount of the high boiling solvent is too small, for example, dye components may precipitate and solidify at the tip of the slit nozzle, causing foreign matter defects, and if it is too large, the drying speed of the composition slows down, and the color described later In the filter manufacturing process, there is a concern that it may cause problems such as poor tact in the vacuum drying process and pin marks of prebake.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers, and in this case, it is not necessary to separately contain a solvent having a boiling point of 150 ° C. or higher. ..
The colored resin composition of the present invention may be subjected to a color filter production by an inkjet method, but in the color filter production by an inkjet method, the ink emitted from the nozzle is very small, several to several tens of pL. Before landing around the nozzle opening or in the pixel bank, the solvent tends to evaporate and the ink tends to concentrate and dry. In order to avoid this, it is preferable that the boiling point of the solvent is high, and specifically, it is preferable that the solvent (B) contains a solvent having a boiling point of 180 ° C. or higher. In particular, it is preferable to contain a solvent having a boiling point of 200 ° C. or higher, particularly preferably a boiling point of 220 ° C. or higher. The high boiling point solvent having a boiling point of 180 ° C. or higher is preferably 50% by mass or more in the solvent (B). By setting the value to the lower limit or more, the effect of preventing evaporation of the solvent from the ink droplets tends to be sufficiently exhibited.

The content ratio of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit thereof is usually 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less, and is used for coating. Considering suitable viscosity and the like, it is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.

[(C) Binder resin]
In the colored resin composition of the present invention, the binder resin (C) is not limited as long as it is soluble in the above-mentioned solvent and can form a cured film having a sufficient degree of curing, but the pattern is formed by alkaline development. From the viewpoint of forming, an alkali-soluble resin is preferable. For example, JP-A-7-207211, JP-A-8-259876, JP-A-10-300922, JP-A-11-140144, JP-A-11-174224, JP-A-2000-56118, The polymer compounds described in each publication such as JP-A-2003-233179 can be used, and among them, the following resins (C-1) to (C-5) are preferable.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. An alkali-soluble resin (hereinafter referred to as "resin (C-1)") obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction may be used. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter, may be referred to as "resin (C-2)").
(C-3): A resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group portion of the resin (C-2) (hereinafter, may be referred to as "resin (C-3)").
(C-4): (Meta) acrylic resin (hereinafter, may be referred to as "resin (C-4)")
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter, may be referred to as "resin (C-5))."
Of these, resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be any as long as they are dissolved by an alkaline developer and have a solubility to the extent that the desired developing treatment can be carried out. It is the same as that described as the same item in Japanese Patent Publication No. 2009-025813. The same applies to the preferred embodiment.
(C-1): With respect to a polymer of an epoxy group-containing (meth) acrylate and another radically polymerizable monomer, unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. An epoxy group is used as one of the particularly preferable resins of the alkali-soluble resin resin (C-1) obtained by adding a polybasic acid anhydride to at least a part of the added resin or the hydroxyl group generated by the addition reaction. The polymer containing 5 to 90 mol% of the (meth) acrylate and 10 to 95 mol% of the other radically polymerizable monomer is unsaturated to 10 to 100 mol% of the epoxy group contained in the copolymer. Examples thereof include a resin obtained by adding a monobasic acid, or an alkali-soluble resin obtained by adding a polybasic acid anhydride to 10 to 100 mol% of the hydroxyl groups generated by the addition reaction.

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 (meth) acrylate. ) Acrylate glycidyl ether and the like can be exemplified. Of these, glycidyl (meth) acrylate is preferable. One of these epoxy group-containing (meth) acrylates may be used alone, or two or more thereof may be used in combination.

The other radically polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effect of the present invention is not impaired, and for example, vinyl aromatics, dienes, (meth). Acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides and the like can be mentioned, and in particular, mono (meth) having a structure represented by the following formula (III). Acrylic is preferred.

The repeating unit derived from the mono (meth) acrylate having the structure represented by the following formula (III) contains 5 to 90 mol% of the repeating units derived from "another radically polymerizable monomer". It is preferable that the content is preferably 10 to 70 mol%, more preferably 15 to 50 mol%, and particularly preferably 15 to 50 mol%.

In the above formula (III), R ⁸⁹ represents a hydrogen atom or a methyl group, and R ⁹⁰ represents a structure represented by the following formula (IV).

In the above formula (IV), R ⁹¹ to R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. In addition, 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, which may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among them, as the structure represented by the formula (IV), the structure represented by the following structural formulas (IVa), (IVb), or (IVc) is particularly preferable.

As the mono (meth) acrylate having the structure represented by the formula (IV), one type may be used alone, or two or more types may be used in combination.
As the "other radically polymerizable monomer" other than the mono (meth) acrylate having the structure represented by the formula (IV), the colored resin composition can be improved in excellent heat resistance and strength. , Styrene, (meth) acrylate-n-butyl, (meth) acrylate-tert-butyl, (meth) acrylate cyclohexyl, (meth) acrylate isoboronyl, (meth) acrylate adamantyl, (meth) acrylate benzyl , (Meta) -2-hydroxyethyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The content of the repeating unit derived from at least one selected from the above-mentioned monomer group is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.
A known solution polymerization method is applied to the copolymerization reaction between the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer.
In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radically polymerizable monomer includes a repeating unit of 5 to 90 mol% derived from the epoxy group-containing (meth) acrylate, and the like. The radically polymerizable monomer of the above is preferably composed of 10 to 95 mol% of the repeating unit, more preferably 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and 30 to 30 to 20 of the former. Those consisting of 70 mol% and the latter 70 to 30 mol% are particularly preferable.

Within the above range, the amount of the polymerizable component and the alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
An unsaturated monobasic acid (polymerizable component) is further reacted with a polybasic acid anhydride (alkali-soluble component) on the epoxy group portion of the epoxy group-containing copolymer synthesized as described above.
Here, as the unsaturated monobasic acid added to the epoxy group, known ones can be used, and examples thereof include unsaturated carboxylic acids having an ethylenically unsaturated double bond.

Specific examples include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and the α-position is substituted with a haloalkyl group, an alkoxyl group, a halogen atom, a nitro group, a cyano group, or the like. Examples thereof include monocarboxylic acids such as (meth) acrylic acid. Of these, (meth) acrylic acid is preferable. These may be used alone or in combination of two or more.

By adding such a component, the binder resin used in the present invention can be imparted with polymerizable properties.
These unsaturated monobasic acids are usually added to 10 to 100 mol% of the epoxy group of the copolymer, preferably 30 to 100 mol%, more preferably 50 to 100 mol%. When it is within the above range, it is preferable because the colored resin composition is excellent in stability over time. As a method for adding an unsaturated monobasic acid to the epoxy group of the copolymer, a known method can be adopted.

Further, known polybasic acid anhydrides can be used as the polybasic acid anhydride added to the hydroxyl group generated when unsaturated monobasic acid is added to the epoxy group of the copolymer.
For example, dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride; trimellitic anhydride, pyromellitic anhydride, benzophenone. Examples thereof include acid anhydrides having three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. One of these polybasic acid anhydrides may be used alone, or two or more thereof may be used in combination.

By adding such a component, alkali solubility can be imparted to the binder resin used in the present invention.
These polybasic acid anhydrides are usually added to 10 to 100 mol% of the hydroxyl groups generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30-80 mol%.

When it is within the above range, the residual film ratio and solubility at the time of development are sufficient, which is preferable.
As a method for adding the polybasic acid anhydride to the hydroxyl group, a known method can be adopted.
Further, in order to improve the photosensitivity, after the above-mentioned polybasic acid anhydride is added, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl groups. May be. The structure of such a resin is described in, for example, Japanese Patent Application Laid-Open No. 8-297366 and Japanese Patent Application Laid-Open No. 2001-89533.

The polystyrene-equivalent weight average molecular weight (Mw) of the above-mentioned binder resin (C) measured by GPC (gel permeation chromatography) is preferably 3000 or more, more preferably 5000 or more, and preferably 100,000 or less, preferably 50,000 or less. The following is more preferable, 30,000 or less is further preferable, and 10,000 or less is particularly preferable. When it is within the above range, it is preferable in that heat resistance, film strength, and solubility in a developing solution are good.
As a guideline for the molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

The acid value of the binder resin (C) is preferably 10 mg-KOH / g or more, more preferably 30 mg-KOH / g or more, further preferably 50 mg-KOH / g or more, and preferably 200 mg-KOH / g or less. 150 mg-KOH / g or less is more preferable, and 100 mg-KOH / g or less is further preferable. When it is set to the lower limit value or more, the solubility in a developing solution tends to be good, and when it is set to the upper limit value or less, the film roughness tends to be suppressed.

The content ratio of the binder resin (C) in the colored resin composition is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more. It is preferable, 80% by mass or less is preferable, 60% by mass or less is more preferable, 50% by mass or less is further preferable, 40% by mass or less is further preferable, and 30% by mass or less is particularly preferable. When it is set to the lower limit value or more, an appropriate film thickness for pattern formation by development tends to be secured, and when it is set to the upper limit value or less, the sensitivity tends to be appropriate for pattern formation by development.

[(D) Polymerizable Monomer]
The colored resin composition of the present invention preferably contains (D) a polymerizable monomer. The polymerizable monomer (D) is not particularly limited as long as it is a polymerizable low molecular weight compound, but may be referred to as an addition polymerizable compound having at least one ethylenic double bond (hereinafter, referred to as “ethylenic compound”). There is.).
The ethylenic compound is a compound having an ethylenic double bond such that when the colored resin composition of the present invention is irradiated with active light, it is addition-polymerized and cured by the action of a photopolymerization initiating component described later. The (D) polymerizable monomer in the present invention means a concept opposite to a so-called polymer substance, and includes dimers, trimers, and oligomers in addition to monomers in a narrow sense.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated bonds contained in the polyfunctional ethylenically monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 5 or more, and preferably 15 or less. More preferably, the number is 10 or less. When it is at least the above lower limit value, the polymerizable property tends to be improved and the sensitivity tends to be high, and when it is at least the above upper limit value, the developability tends to be better.

Examples of the ethylenic compound in the (D) polymerizable monomer include unsaturated carboxylic acids such as (meth) acrylic acid; esters of monohydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds and unsaturated carboxylic acids. Esters; Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Estherization of unsaturated carboxylic acids with polyvalent carboxylic acids and polyvalent hydroxy compounds such as the above-mentioned aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds. Examples thereof include an ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound; and the like.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylol propanetri (meth) acrylate, and trimethylol ethanetri (meth) acrylate. , Pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) Examples thereof include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. Further, an itaconic acid ester in which the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid moiety, a crotonic acid ester in which the crotonic acid moiety is replaced, a maleic acid ester in which the maleic acid moiety is replaced, or the like. Can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcindi (meth) acrylate, and pyrogalloltri (meth) acrylate.
The ester obtained by the esterification reaction of the unsaturated carboxylic acid with the polyvalent carboxylic acid and the polyvalent hydroxy compound may be a single substance or a mixture. Typical examples are (meth) acrylic acid, phthalic acid, and ethylene glycol condensates; (meth) acrylic acid, maleic acid, and diethylene glycol condensates; (meth) acrylic acid, terephthalic acid, and pentaerythritol condensation. Substances; Examples thereof include (meth) acrylic acid, adipic acid, butanediol, and condensates of glycerin.

Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound with a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; and alicyclics such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanate; aromatic diisocyanates such as tolylene diisocyanate and diphenylmethane diisocyanate, and (meth) acryloyl such as 2-hydroxyethyl (meth) acrylate and 3-hydroxy [1,1,1-tri (meth) acryloyloxymethyl] propane. Examples thereof include a reaction product with a group-containing hydroxy compound.

Other examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylenebis (meth) acrylamide; allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinylphthalate. ..
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferable, pentaerythritol or dipentaerythritol (meth) acrylic acid esters are more preferable, and dipentaerythritol hexa (meth) acrylates are particularly preferable.

Further, the ethylenic compound may be a monomer having an acid value. Examples of the monomer having an acid value are esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an acid is obtained by reacting an unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride. A polyfunctional monomer having a group is preferable, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

Although one kind of these monomers may be used alone, a mixture of two or more kinds may be used because it is difficult to obtain a single compound in production.
Further, if necessary, (D) a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as the polymerizable monomer.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

Within the above range, the developing and dissolving characteristics are less likely to deteriorate, and manufacturing and handling are easy. Further, it is preferable because the photopolymerization performance does not deteriorate easily and the curability such as the surface smoothness of the pixel is good.
In the present invention, the polyfunctional monomer having a more preferable acid group is, for example, a mixture containing, for example, a succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentaacrylate as a main component. This polyfunctional monomer can also be used in combination with other polyfunctional monomers.

In the colored resin composition of the present invention, the content ratio of these (D) polymerizable monomers is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, still more preferable, in the total solid content. Is 18% by mass or more, and is usually 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less.
The ratio of the (D) polymerizable monomer to 100 parts by mass of the (A) coloring material is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, still more preferably 30 parts by mass or more. It is still more preferably 40 parts by mass or more, particularly preferably 45 parts by mass or more, and usually 500 parts by mass or less, preferably 200 parts by mass or less, and more preferably 100 parts by mass or less.
Within the above range, photocuring is moderate, adhesion failure during development is difficult to place, the cross section after development is difficult to form a reverse taper shape, and peeling phenomenon / removal failure due to reduced solubility is difficult to place. preferable.

[(E) Photopolymerization initiation component and (E') Thermal polymerization initiation component]
The colored resin composition of the present invention preferably contains at least one of (E) a photopolymerization initiation component and (E') a thermal polymerization initiation component 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 contains a resin having an ethylenic double bond as the component (C) or contains an ethylenic compound as the component (D), it directly absorbs light or absorbs light. It is preferable to contain at least one of a photopolymerization initiating component having a function of photosensitizing and causing a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical and a thermal polymerization initiating component of generating a polymerization active radical by heat. .. In the present invention, the component (E) as the photopolymerization initiator is a photopolymerization initiator (hereinafter, optionally also referred to as “(E1) component”) and a polymerization accelerator (hereinafter, optionally, “(E2) component”). ”), A sensitizing dye (hereinafter, optionally also referred to as“ (E3) component ”) and other additives are used in combination.

[(E) Photopolymerization initiation component]
The (E) photopolymerization initiator component in the present invention is a mixture of (E1) a photopolymerization initiator and an additive such as (E2) polymerization accelerator and (E3) sensitizing dye added as needed. It is a component having a function of directly absorbing light or being photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical.

Examples of the (E1) photopolymerization initiator constituting the photopolymerization initiator include the titanosen derivatives described in JP-A-59-152396, JP-A-61-15119, and the like; JP-A-10-300922. Hexaarylbiimidazole derivatives described in JP-A, JP-A-11-174224, JP-A-2000-56118, etc .; Radical activators such as s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone Derivatives; Examples thereof include oxime ester-based derivatives described in JP-A-2000-80068.

Specific examples thereof include the photopolymerization initiator described in International Publication No. 2009/107734 and the like.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone and O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazole-3-yl] Ethanone oxime and compounds represented by the following formula (V) can be mentioned.

(In the formula (V), R ¹⁰¹ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms or a heteroaryl group having 4 to 25 carbon atoms. They represent alkyl groups, all of which may have substituents, or R ¹⁰¹ may be attached to X or Z to form a ring.
R ¹⁰² has an alkanoyl group having 2 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, an allylloyl group having 7 to 20 carbon atoms, and an alkoxycarbonyl group having 2 to 10 carbon atoms. , An aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, a heteroallyloyl group having 3 to 20 carbon atoms or an alkylaminocarbonyl group having 2 to 20 carbon atoms, all of which are shown. It may have a substituent.

X represents at least one of a divalent aromatic hydrocarbon ring group and an aromatic complex group formed by condensing two or more rings which may have a substituent.
Z indicates an aromatic ring group which may have a substituent. )
Among the compounds represented by the formula (V), a compound having a carbazole ring in which X may have a substituent is preferable, and specifically, a compound represented by the following formula (VI) is used. Among them, the compound represented by the following formula (VII) is particularly preferable.

In formula (VI), R ¹⁰¹ , R ¹⁰² and Z are synonymous with the definitions in formula (V). R ¹⁰³ to R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

In the formula (VII), R ^101a represents an alkyl group having 1 to 3 carbon atoms or a group represented by the following formula (VIIa).

In formula (VIIa), R ¹¹⁰ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, or a heteroarylalkyl group having 4 to 25 carbon atoms. Shows the group. * Represents a binding site.
R ^102a represents an alkanoyl group having 2 to 4 carbon atoms, and X ^a represents a 3,6-carbazolyl group in which the nitrogen atom may be substituted with an alkyl group of 1 to 4 carbon atoms. Z ^a represents a naphthyl group which may be substituted with a phenyl group or a morpholino group which may be substituted with an alkyl group.

Commercially available products may be used as the oxime-based initiator. Examples of commercially available products include OXE-01, OXE-02 (manufactured by BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Tsunyu Powerful Electronic New Materials Limited). A company (manufactured by CANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)) can be mentioned.

Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanol, 2-ethylthioxanthone, 2 , 4-Dixanthone derivatives such as diethylthioxanthone, benzoic acid ester derivatives, aclysine derivatives, phenylazine derivatives, anthrone derivatives and the like. Commercially available products may be used as these initiators.

Examples of commercially available products include IRGACURE 651, IRGACURE 184, DAROCURE 1173, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 379EG, LUCIRIN TPO, and IRGACURE 8 Is a registered trademark) and the like.

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester-based derivatives are more preferable. In particular, oxime ester-based derivatives are preferable.
Examples of the (E2) polymerization accelerator used as needed include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester; 2-mercaptobenzothiazole, 2-mercapto. Examples thereof include mercapto compounds having a heterocycle such as benzoxazole and 2-mercaptobenzimidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds.

As these (E1) photopolymerization initiator and (E2) polymerization accelerator, one type may be used alone, or two or more types may be used in combination.
Further, the (E3) sensitizing dye is used for the purpose of increasing the sensitivity, if necessary. An appropriate sensitizing dye is used depending on the wavelength of the image exposure light source. For example, the xanthene dyes described in JP-A-4-221958, JP-A-4-219756, etc .; JP-A-3- Cmarin-based dyes having a heterocycle described in JP-A-239703, JP-A-5-289335, etc .; 3-Ketokumarin-based dyes 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-A-45-373777, JP-A-48-84183, JP-A. Japanese Patent Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88805, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-16888 , JP-A-5-107761, JP-A-5-210240, JP-A-4-288818, and the like, and examples thereof include dyes having a dialkylaminobenzene skeleton.
(E3) The sensitizing dye may also be used alone or in combination of two or more.

In the colored resin composition of the present invention, the content ratio of these (E) photopolymerization initiation components is usually 0.1% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass in the total solid content. % Or more, more preferably 1.5% by mass or more, still more preferably 1.8% by mass or more, particularly preferably 2% by mass or more, and usually 40% by mass or less, preferably 30% by mass or less. It is preferably 20% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. When it is set to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and when it is set to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer and the accompanying development defect can be suppressed. There is.

In the colored resin composition of the present invention, the content ratio of these (E1) photopolymerization initiators is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1% by mass or more in the total solid content. More preferably, 1.5% by mass or more is further preferable, 1.8% by mass or more is particularly preferable, 40% by mass or less is more preferable, 30% by mass or less is more preferable, and 20% by mass or less is further preferable. 10% by mass or less is more preferable, and 5% by mass or less is particularly preferable. When it is set to the lower limit value or more, the decrease in sensitivity to the exposed light tends to be suppressed, and when it is set to the upper limit value or less, the decrease in the solubility of the unexposed portion in the developer and the accompanying development failure are suppressed. There is a tendency to be able to do it.

[(E') Thermal polymerization initiation component]
Specific examples of the (E') thermal polymerization initiator component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, hydrogen peroxide and the like. Of these, azo compounds are preferably used. More specifically, for example, the thermal polymerization initiation component described in International Publication No. 2009/107734 and the like can be used.
These thermal polymerization initiation components may be used alone or in combination of two or more.

[Other optional ingredients]
The colored resin composition of the present invention may contain a quenching agent and an antioxidant in addition to the above-mentioned components. Further, at least one of the surfactant, the organic carboxylic acid and the organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a heat polymerization inhibitor, a storage stabilizer, a surface protectant, an adhesion improver, a development improver and the like can be used. It may be contained. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. When the pigment is contained, a dispersant or a dispersion aid may be contained.

[Quenching agent]
The photochromic agent is not particularly limited as long as it has absorption in the vicinity of the fluorescence wavelength emitted by the xanthene dye represented by the general formula (I), and is, for example, a metal complex salt dye, an anthraquinone dye, or a phthalocyanine dye. , Tetraazaporphyrin dyes, triarylmethane dyes, metal complex salt dyes and the like are preferably mentioned.

The metal complex salt dye is a dye obtained by complexing a dye molecule containing a group capable of complex chloride with a metal atom in the molecule and a metal atom.

Specific examples of the metal complex salt dye include, for example, C.I. I. Solvent Yellow 13, 19, 21, 25, 25: 1, 62, 79, 81, 82, 83, 83: 1, 88, 89, 90, 151, 161; C.I. I. Solvent Orange 5, 11, 20, 40: 1, 41, 45, 54, 56, 58, 62, 70, 81, 99; C.I. I. Solvent Red 8, 35, 83: 1, 84: 1, 90, 90: 1, 91, 92, 118, 119, 122, 124, 125, 127, 130, 132, 160, 208, 212, 214, 225, 233, 234, 243; C.I. I. Solvent Violet 2, 21, 21: 1, 46, 49, 58, 61; C.I. I. Solvent Blue 137; C.I. I. Solvent Brown 28, 42, 43, 44, 53, 62, 63; C.I. I. Acid Yellow 59, 121; C.I. I. Acid Orange 74, 162; C.I. I. Examples thereof include the metal complex salt dyes described in Acid Red 211, JP-A-2010-170117, and JP-A-2013-7032. These may be used alone or in combination of two or more.

Examples of the dye molecule (ligand) include azo dyes and methine dyes, and azo dyes are preferable. Examples of the metal atom include chromium, cobalt, nickel and the like, and chromium and cobalt are preferable.
Examples of the metal complex salt dye include a 1: 1 type metal complex salt dye having a bond ratio of a metal atom and a dye molecule of 1: 1 and a 1: 2 type metal complex salt dye having a ratio of 1: 2. 1: 2 type metal complex salt dye is preferable.

Examples of the anthraquinone dye include C.I. I. Bat Blue 4, C.I. I. Acid Blue 23, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 40, C.I. I. Acid Blue 41, C.I. I. Acid Blue 43, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 78, C.I. I. Acid Blue 80, C.I. I. Acid Blue 112, C.I. I. Acid Blue 138, C.I. I. Acid Blue 182, C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 12, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45, C.I. I. Solvent Blue 59, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 94, C.I. I. Solvent Blue 97, C.I. I. Solvent Blue 101, C.I. I. Solvent Blue 104, C.I. I. Solvent Blue 122, C.I. I. Reactive Blue 4, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse Blue 56, C.I. I. Examples thereof include those described in Disperse Blue 60, International Publication No. 2014/012814, JP-A-2017-2257, and the like.

Examples of the phthalocyanine dye include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Bat blue 5 and the like can be mentioned.

Examples of the tetraazaporphyrin dye include those described in International Publication No. 2014/0128814.

Further, as the triarylmethane dye, for example, C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Examples thereof include those described in Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, International Publication No. 2015/08217, and the like.

The content ratio of the quencher in the colored resin composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and 3% by mass or more in the total solid content. Further, 4% by mass or more is particularly preferable, 50% by mass or less is preferable, 30% by mass or less is more preferable, 10% by mass or less is further preferable, and 6% by mass or less is particularly preferable. When the value is not less than the lower limit, the contrast tends to be improved, and when the value is not more than the upper limit, the decrease in brightness tends to be suppressed.

[Antioxidant]
The antioxidant means a compound that suppresses a decrease in the brightness of a dye such as a xanthene dye represented by the general formula (I). It is not particularly limited as long as it can suppress the decrease in the brightness of the dye, but it has a high ability to capture peroxy radicals that promote the decomposition of the dye, and has high compatibility with the colored resin composition, and is available. The compound represented by the following formula (i) is preferable because it is easy.

In the above formula, ^RA and ^RB each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent.
L represents a hydrogen atom, a carbon atom, a sulfur atom, an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent.
Z represents a divalent group consisting of an alkylene group having 1 to 10 carbon atoms and / or an ester bond which may have a substituent.

The benzene ring in the above formula may have any substituent other than ^RA and ^RB , —OH, and Z.
m represents an integer of 1 to 4.
When m is an integer of 2 or more, a plurality of molecules contained in one molecule.

May have the same structure or may be different (* represents a binding site with L).

( ^RA and ^RB )
^RA and ^RB each independently represent an alkyl group having 1 to 12 carbon atoms which may have a substituent.
The alkyl group may be linear or branched, but is preferably a branched alkyl group from the viewpoint of high peroxy radical scavenging ability and stable chemical structure after scavenging.
Further, the number of carbon atoms is preferably 1 to 20, more preferably 3 to 10, from the viewpoint that many chemically conjugated structures can be obtained because it is stable after radical scavenging.

(L)
L represents a hydrogen atom, a carbon atom, a sulfur atom, an aromatic ring group which may have a substituent, or a heterocyclic group which may have a substituent.
Examples of the aromatic ring in L include an aromatic hydrocarbon ring and an aromatic heterocycle.
The aromatic hydrocarbon ring may be a monocyclic ring or a fused ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 10, but for example, m free atomic values can be used. Examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

The aromatic heterocycle may be a monocyclic ring or a fused ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 3 to 10, but for example, m free atomic values. Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrol ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloymidazole ring, pyrrolopyrazole ring, pyrrolopyrazole ring, thienopyrrole ring. , Thienothiophene ring, flopirol ring, flofran ring, thienoflan ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline Examples thereof include a ring, a quinoxaline ring, a phenanthridin ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

The free valence in the present invention is based on the description in "Organic Chemistry / Biochemical Nomenclature" (Nanedo, May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pp. 11-12). Is.
On the other hand, the heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the atom other than carbon constituting the heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. When the heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.

Specific examples thereof include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimideyl group, a piperidinyl group, a pyrrolidinyl group and the like.
Among the aromatic rings and heterocycles in L, it is represented by the following <Group A> in that it has excellent compatibility with a binder resin or the like in a colored resin composition and has a stable structure after radical scavenging. Radicals are particularly preferred.

Each * in the above structure independently represents a binding site with Z, as well as a hydrogen atom or any substituent. However, in each ring, at least one of * represents a binding site with Z.

(Z)
Z is a divalent group consisting of an alkylene group having 1 to 10 carbon atoms and / or an ester bond which may have a substituent.
That is, Z may be formed of only an alkylene group having 1 to 10 carbon atoms which may have a substituent or an ester bond, and may have a substituent and an alkylene having 1 to 10 carbon atoms. It may be a group combined with an ester bond.
The combined groups also include, for example, -CH ₂ -C (= O) O-CH _2- , and the like.

The number of constituent atoms of Z is preferably 30 or less. Further, the alkylene group having 1 to 10 carbon atoms preferably has 1 to 5 carbon atoms, and more preferably 1 or 2 carbon atoms, from the viewpoint of ease of synthesis reaction.
The benzene ring in the formula (i) may have any substituent other than ^RA , ^RB , -OH, and Z, but the substituent has a high bonding force with a radical. It is preferable not to have.
Examples of the substituents that the alkyl group in ^RA and ^RB , the aromatic ring group and heterocyclic group in L, the alkylene group in Z, and the benzene ring in the above formula may have are as follows (substitution group W2). Can be mentioned.

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group with 1 to 8 carbon atoms, alkenyl group with 2 to 8 carbon atoms, alkoxyl group with 1 to 8 carbon atoms, phenyl group, mesityl group, trill group, naphthyl group, cyano group, acetyloxy Group, alkylcarboxyl group with 2-9 carbon atoms, sulfonic acid amide group, sulfonalkylamide group with 2-9 carbon atoms, alkylcarbonyl group with 2-9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, carbon A dialkylaminoethyl group, a trifluoromethyl group, a trialkylsilyl group having 1 to 8 carbon atoms, a nitro group, and an alkylthio group having 1 to 8 carbon atoms to which an alkyl group having 1 to 4 numbers is bonded.

(M)
M in the formula (i) represents an integer of 1 to 4.
From the viewpoint of high solubility in a solvent and high radical scavenging ability, m is preferably 2 to 4.

The compound represented by the formula (i) is preferably a compound represented by the following formula (i') from the viewpoint of further improving the antioxidative ability.

In the above formula, ^RA and ^RB , L, and m are synonymous with those in the above formula (i).
n represents an integer of 1 to 10.
l represents an integer from 0 to 5.
The benzene ring in the above formula may have any substituent other than ^RA and ^RB , −OH, and − (CH ₂ ) _n −.
When l is 1 or more, the order of −CH _2- and −C (= O) O− is in no particular order.
When m is an integer of 2 or more, a plurality of molecules contained in one molecule.

May have the same structure or may be different.
* Represents the binding site with L.

(N)
n represents an integer of 1 to 10.
It is preferably an integer of 1 to 5 from the viewpoint of high compatibility with the binder resin and the like and good antioxidant performance.

(About l)
l represents an integer from 0 to 5.
It is preferably an integer of 0 to 1 from the viewpoint of high compatibility with the binder resin and the like and good antioxidant performance.

(Molecular weight)
The molecular weight of the antioxidant is not particularly limited, but is usually 90 or more, preferably 150 or more, more preferably 250 or more, and usually 3000 or less, preferably 2000 or less, still more preferably 1300 or less. Within the above range, the bonding force with radicals is high, which is preferable.

(Concrete example)
Among the compounds represented by the formula (i), preferable specific examples are shown below.

Among these, IRGANOX1010, IRGANOX1035, IRGANOX1330 or ADEKA STAB AO-20 are preferable, IRGANOX1010, IRGANOX1035, or IRGANOX1330 is more preferable, and IRGANOX1010 is even more preferable, from the viewpoint of high antioxidant capacity.

The content ratio of the antioxidant is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass or more, and 2% by mass or more in the total solid content. More preferably, 3% by mass or more is particularly preferable, 10% by mass or less is preferable, 8% by mass or less is more preferable, 6% by mass or less is further preferable, and 5% by mass or less is particularly preferable. Within the above range, it is preferable in that it is well dispersed in the colored resin composition, less unnecessary substances are deposited, a high antioxidative ability is exhibited, and a decrease in luminance can be suppressed.

[Dispersant]
When the colored resin composition of the present invention contains a pigment, it is preferable that the colored resin composition further contains a dispersant.
The dispersant in the present invention is not particularly limited as long as the pigment can be dispersed and stable.
For example, cationic, anionic, nonionic, amphoteric and other dispersants can be used, but polymer dispersants are preferred. Specific examples thereof include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate ester salts of polymer copolymers, and cationic comb-type graft polymers. Among these dispersants, block copolymers, polyurethanes, and cationic comb-type graft polymers are preferable. Particularly, a block copolymer is preferable, and among these, a block copolymer composed of an A block having a solvent-friendly property and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, as the B block having a nitrogen atom-containing functional group, a unit structure having at least one of a quaternary ammonium base and an amino group in the side chain can be mentioned, while the quaternary A block has a quaternary solvent. Unit structures that do not have ammonium bases and amino groups can be mentioned.
The B block constituting the acrylic block copolymer has a unit structure having at least one of a quaternary ammonium base and an amino group, and is a site having a pigment adsorption function.

When the quaternary ammonium base is contained as the B block, the quaternary ammonium base may be directly bonded to the main chain, or may be bonded to the main chain via a divalent linking group. ..
Examples of such block copolymers include those described in JP-A-2009-025813.

Further, the colored resin composition of the present invention may contain a dispersant other than those described above. Examples of other dispersants include those described in JP-A-2006-343648.
When the colored resin composition of the present invention contains a pigment, the content ratio of the dispersant is 2 to 1000 parts by mass, particularly 5 to 500 parts by mass, and particularly 10 to 250 parts by mass with respect to 100 parts by mass of the total content of the pigment. It is preferable to use it so as to be within the range of parts by mass.
Within the above range, good pigment dispersibility can be ensured, and the dispersion stability of the pigment becomes better, which is preferable.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid referred to here may be a pigment derivative, and examples of the pigment derivative include JP-A-2001-22520, JP-A-2001-271004, JP-A-2002-179766, and JP-A-2007-. Various compounds and the like described in Japanese Patent Application Laid-Open No. 113000 and Japanese Patent Application Laid-Open No. 2007-186681 can be used.

The content ratio of the dispersion aid in the colored resin composition of the present invention is usually 0.1% by mass or more, usually 30% by mass or less, preferably 20% by mass or less, based on the total solid content of the pigment. It is preferably 10% by mass or less, more preferably 5% by mass or less. By controlling the addition amount within the above range, the effect as a dispersion aid is exhibited, and it is preferable in that the dispersibility and dispersion stability are better.

[Preparation method of colored resin composition]
In the present invention, the colored resin composition can be prepared by an appropriate method, and for example, the (A) coloring material and the (C) binder resin containing the xanthene dye represented by the general formula (I). Can be prepared by mixing (B) with a solvent and, if necessary, any component used.

Further, a color material-containing liquid containing (A) a color material and (B) a solvent may be prepared, and (C) a binder resin and an arbitrary component may be mixed therewith.
As a preparation method when a pigment is contained, for example, paint is used in a solvent containing the pigment in the presence of a dispersant and a dispersion aid added as needed, in some cases together with a part of the (C) binder resin. A pigment dispersion is prepared by mixing and dispersing while pulverizing using a shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, or the like. In the pigment dispersion, a xanthene dye (I), (C) a binder resin,, if necessary, (D) a polymerizable monomer, (E) at least one of a photopolymerization initiation component and a thermal polymerization initiation component, and the like are added. Examples thereof include a method of preparing by adding and mixing.
On the other hand, when the pigment is not contained, for example, when only the dye is used as the coloring material, the coloring resin does not require a dispersant or a dispersion aid and does not require a complicated pigment dispersion step. The composition can be produced at low cost.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state in which all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto the substrate, and constituent members such as a color filter, a liquid crystal display device, and an organic EL display device are formed.
Hereinafter, as an application example of the colored resin composition of the present invention, an application of a color filter as a pixel and an image display device using them will be described. Specific examples of the image display device include a liquid crystal display device (panel) and an organic EL display device.

<Color filter>
The color filter of the present invention has pixels formed by using the colored resin composition of the present invention.
Hereinafter, a method for forming the color filter of the present invention will be described.
The pixels of the color filter can be formed by various methods. Here, a case of forming by a photolithography method using a photopolymerizable colored resin composition will be described as an example, but the production method is not limited to this.

First, a black matrix is formed on the surface of the substrate so as to partition the portion forming the pixel, if necessary, and the colored resin composition of the present invention is applied onto the substrate and then prebaked. The solvent is evaporated to form a coating film. Next, the coating film is exposed via a photomask, then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film, and then post-baked to obtain red, green, and blue colors. A color filter can be produced by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixels formed by using the colored resin composition of the present invention are red pixels.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has appropriate strength, but for example, a polyester resin, a polyolefin resin, a polycarbonate resin, an acrylic resin, and a thermoplastic resin. Examples include sheets, epoxy resins, thermoplastic resins, and various types of glass.

Further, if desired, these substrates may be subjected to appropriate pretreatment such as a thin film forming treatment with a silane coupling agent or a urethane resin, a surface treatment such as a corona discharge treatment or an ozone treatment.
When the colored resin composition is applied to the substrate, examples thereof include a spinner method, a wire bar method, a flow coat method, a slit and spin method, a die coat method, a roll coat method, and a spray coat method. Of these, the slit-and-spin method and the die coat method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, and particularly preferably 0.8 to 5.0 μm as the film thickness after drying.
Within the above range, it is preferable in that the gap adjustment in the pattern development and the liquid crystal cell formation step is easy, and the desired color development is easy.
As the radiation used for exposure, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

The light source for using the radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited, but for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and the like. Lamp light sources such as medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; laser light sources such as argon ion lasers, YAG lasers, excima lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers can be mentioned. An optical filter can also be used when irradiating light of a specific wavelength for use.

The exposure amount of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkaline developing solution include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, and sodium phosphate. Inorganic alkaline compounds such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide; mono-ethanolamine, di-ethanolamine, tri-ethanolamine, mono-methylamine, Di-methylamine, tri-methylamine, mono-ethylamine, di-ethylamine, tri-ethylamine, mono-isopropylamine, di-isopropylamine, n-butylamine, mono-isopropanolamine, di-isopropanolamine, tri-isopropanolamine , Ethyleneimine, ethylenedimin, tetramethylammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline is preferable.

An appropriate amount of a water-soluble organic solvent such as isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol, or a surfactant can be added to the alkaline developer. After alkaline development, it is usually washed with water.
As the developing method, any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like can be used. The developing conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

The conditions of the development process are not particularly limited, but the development temperature is usually in the range of 10 ° C. or higher, particularly 15 ° C. or higher, further 20 ° C. or higher, and usually 50 ° C. or lower, particularly 45 ° C. or lower, further 40 ° C. or lower. Is preferable. The developing method can be any one of a dipping developing method, a spray developing method, a brush developing method, an ultrasonic developing method and the like.

When the color filter produced in this way is used in a liquid crystal display device, a transparent electrode such as ITO is formed on the image in this state as it is, and used as a part of parts such as a color display and a liquid crystal display device. Although it is used, in order to improve surface smoothness and durability, a top coat layer such as polyamide or polyimide can be provided on the image if necessary. Further, in some applications such as a plane orientation type drive system (IPS mode), a transparent electrode may not be formed. Further, in the vertically oriented drive system (MVA mode), ribs may be formed. Further, instead of the bead spraying type spacer, a pillar structure (photospacer) by a photolithography method may be formed.

<Image display device>
The image display device of the present invention has the above-mentioned color filter of the present invention. Examples of the image display device include a liquid crystal display device and an organic EL display device.

<Liquid crystal display device>
The liquid crystal display device of the present invention uses the above-mentioned color filter of the present invention. The model and structure of the liquid crystal display device of the present invention are not particularly limited, and the liquid crystal display device of the present invention can be assembled according to a conventional method using the color filter of the present invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in "LCD Device Handbook" (Nikkan Kogyo Shimbun, published on September 29, 1989, by the 142nd Committee of the Japan Society for the Promotion of Science).

<Organic EL display device>
When creating an organic EL display device having the color filter of the present invention, for example, as shown in FIG. 7, on a transparent support substrate 10 on a blue color filter in which pixels 20 are formed by the colored resin composition of the present invention. A multicolored organic EL element is manufactured by laminating the organic illuminant 500 via the organic protective layer 30 and the inorganic oxide film 40.

As a method of laminating the organic illuminant 500, a method of sequentially forming 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 on the upper surface of the color filter, or Examples thereof include a method of bonding the organic light emitter 500 formed on another substrate onto the inorganic oxide film 40. The organic EL element 100 produced in this way can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, the present invention will be described in more detail with reference to synthetic examples, examples and comparative examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.
<Dye synthesis>
(Synthesis Example 1: Synthesis of Dye A)
{Synthesis of compound 1}

Under a nitrogen atmosphere, 4-chlorophenol (25.0 g, 194 mmol) and 1,4-dibromobutane (69 mL, 582 mmol) were dissolved in acetone (300 mL), and potassium carbonate (53.6 g, 388 mmol) was further added. The mixture was stirred under reflux for 17 hours. The reaction mixture was cooled to room temperature, potassium carbonate was filtered off, and the filtrate was concentrated. The obtained residue was purified by silica gel column chromatography (silica gel 800 mL, developing solvent: hexane 100% to hexane / ethyl acetate = 100/5 (volume ratio)), and compound 1 (31.5 g, yield 61%). Got

{Synthesis of Dye A}

In a nitrogen atmosphere, compound 2 (3.45 g, 6.01 mmol) and compound 1 (6.3 g, 84 mmol) synthesized by the method described in JP2013-253168A were added to N, N-dimethylformamide (40 mL). After dissolution, potassium carbonate (2.1 g, 15.0 mmol) and tetranormal butylammonium bromide (194 mg, 0.60 mmol) were further added, and the mixture was stirred at 80 ° C. for 6 hours. After cooling to room temperature, the reaction solution was added to water (100 mL). The obtained solid was collected by filtration and purified by silica gel column chromatography (silica gel 250 mL, developing solvent: chloroform / methanol = 100/2 (volume ratio)) to obtain dye A (6.5 g, yield 90) as a red amorphous solid. %) Was acquired.
Dye A was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10% by mass. At this time, the maximum absorption wavelength (λmax) was 546 nm, and the gram absorption coefficient (g) was 122.9 g ^-1 cm ^-1 . The results of liquid chromatography-mass spectrometry of this dye A are shown below.
LCMS (ESI, posi) m / z 939 ((M ⁺ C ₅₅ H ₅₂ Cl ₂ N ₂ O ₆ S)

(Synthesis Example 2: Synthesis of Dye B)
{Synthesis of compound 3}

4-Chlorobenzoyl chloride (25.0 g, 143 mmol) and 3-bromo-1-propanol (18.1 g, 130 mmol) were dissolved in ethyl acetate (220 mL) under a nitrogen atmosphere, and triethylamine (36.0 mL) was dissolved under ice-cooling. 260 mmol) was added dropwise, and the mixture was stirred at room temperature for 10 hours. The reaction mixture was washed twice with water (200 mL), and the organic layer was concentrated to obtain a transparent oil-like compound 3 (37.5 g, yield: quantitative).

{Synthesis of Dye B}

Dye B (16.5 g, yield 94%) as a red amorphous solid from compound 2 (10.3 g, 18.0 mmol) and compound 3 (18.0 g, 64.9 mmol) in the same manner as dye A. Was synthesized.
Dye B was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10% by mass. At this time, the maximum absorption wavelength (λmax) was 544 nm, and the gram absorption coefficient (g) was 125.2 g ^-1 cm ^-1 . The results of liquid chromatography-mass spectrometry of this dye B are shown below.
LCMS (ESI, posi) m / z 968 ((M + C ₅₅ H ₄₈ Cl ₂ N ₂ O ₈ S)

(Synthesis Example 3: Synthesis of Dye C)
{Synthesis of compound 4}

In a nitrogen atmosphere, 3-bromo-1-propanol (1.92 g, 13.9 mmol) and p-pentylbenzoyl chloride (2.97 g, 13.9 mmol) were dissolved in ethyl acetate (10 mL) at room temperature, and triethylamine (2) was dissolved. .81 g, 27.9 mmol) was added little by little, and the mixture was stirred as it was at room temperature for 3 hours. After completion of the reaction, water (5 mL) was mixed. After extraction with ethyl acetate, the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to obtain oily compound 4 (4.43 g).

{Synthesis of Dye C}

Compound 2 (1.50 g, 2.6 mmol), Compound 4 (4.43 g, 5.2 mmol), Potassium carbonate (1.25 g, 9.1 mmol), Tetra n-butylammonium bromide (41.9 mg) under a nitrogen atmosphere. , 0.13 mmol) was added with N, N-dimethylformamide (10 mL), heated to 80 ° C., and stirred for 17 hours. After completion of the reaction, the reaction solution was poured into water (20 mL), extracted with chloroform (50 mL), washed with saturated brine, and dried over anhydrous magnesium sulfate. The desiccant was separated by filtration, the solvent was distilled off, and the obtained solid was dissolved in chloroform (2 mL), and silica gel column chromatography (silica gel 100 mL, developing solvent: chloroform / methanol = 100/0 to 97/3 (volume). (Ratio)) was purified to obtain a red solid dye C (1.13 g, yield 42%).
Dye C was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10% by mass. At this time, the maximum absorption wavelength (λmax) was 544 nm, and the gram absorption coefficient (g) was 112 Lg ^-1 cm ^-1 . The results of liquid chromatography-mass spectrometry of this dye C are shown below.
LCMS (ESI, posi) m / z 1039 ((M ⁺ C ₆₅ H ₇₀ N ₂ O ₈ S)

(Synthesis Example 4: Synthesis of Dye D)
{Synthesis of compound 5}

In a nitrogen atmosphere, 3-bromo-1-propanol (1.92 g, 13.9 mmol) and pt-butylbenzoyl chloride (2.73 g, 13.9 mmol) were dissolved in ethyl acetate (10 mL) at room temperature, and triethylamine was dissolved. (2.81 g, 27.9 mmol) was added little by little, and the mixture was stirred as it was at room temperature for 3 hours. After completion of the reaction, water (5 mL) was mixed. After extraction with ethyl acetate, the organic layer was washed with saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The desiccant was filtered off and the solvent was distilled off to obtain oily compound 5 (4.1 g).

{Synthesis of Dye D}

Under nitrogen atmosphere, compound 2 (1.50 g, 2.6 mmol), compound 5 (4.00 g, 5.2 mmol), potassium carbonate (1.25 g, 9.1 mmol), tetra n-butylammonium bromide (82 mg, 0). N, N-dimethylformamide (10 mL) was added to .26 mmol), heated to 80 ° C., and stirred for 17.5 hours. After completion of the reaction, the reaction solution was poured into water (20 mL), extracted with chloroform (50 mL), washed with saturated brine, and dried over anhydrous magnesium sulfate. The desiccant was separated by filtration, the solvent was distilled off, and the obtained solid was dissolved in chloroform (2 mL), and silica gel column chromatography (silica gel 100 mL, developing solvent: chloroform / methanol = 100/0 to 94/6 (volume). (Ratio)) was purified to obtain a red solid dye D (1.36 g, yield 52%).
Dye D was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10% by mass. At this time, the maximum absorption wavelength (λmax) was 544 nm, and the gram absorption coefficient (g) was 110 Lg ^-1 cm ^-1 . The results of liquid chromatograph-mass spectrometry of this dye D are shown below.
LCMS (ESI, posi) m / z 1011 ((M ⁺ C ₆₃ H ₆₆ N ₂ O ₈ S)

(Synthesis Example 5: Synthesis of Resin A)
145 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was stirred while substituting with nitrogen, and the temperature was raised to 120 ° C. Here, 5.2 parts by mass of styrene, 132 parts by mass of glycidyl methacrylate, 4.4 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton and 2.2'-azobis-2-methylbutyro. A mixed solution of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was replaced with air, 1.1 parts by mass of trisdimethylaminomethylphenol and 0.19 parts by mass of hydroquinone were added to 67.0 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Then, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added, and the mixture was reacted at 100 ° C. for 3.5 hours. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the resin solution thus obtained was about 9000, and the acid value was 25 mgKOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content became 40% by mass, and the resin A was used.

(Synthesis Example 6: Synthesis of Resin B)
"NC3000H" (epoxy equivalent 288, softening point 69 ° C., manufactured by Nippon Kayaku Co., Ltd.) 400 parts by mass, 102 parts by mass of acrylic acid, 0.3 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine, and propylene glycol monomethyl 264 parts by mass of ether acetate (PGMEA) was charged into a reaction vessel, and the mixture was stirred at 95 ° C. until the acid value became 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mgKOH / g). Then, 151 parts by mass of tetrahydrophthalic anhydride was further added and reacted at 95 ° C. for 4 hours to obtain a resin solution having an acid value of 102 mgKOH / g and a polystyrene-equivalent weight average molecular weight (Mw) of 3900 measured by GPC. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content was 44% by mass, and the resin B was used.

(Synthesis Example 7: Synthesis of Resin C)
10.4 parts by mass of styrene, 85.3 parts by mass of glycidyl methacrylate, 61.9 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton, 43.2 parts by mass of acrylic acid, tetrahydrophthalic anhydride (THPA) 59.3 parts by mass was used, and the mixture was synthesized by the same method as in Synthesis Example 5. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the resin solution thus obtained was about 8400, and the acid value was 76 mgKOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content became 40% by mass, and the resin C was used.

(Synthesis Example 8: Synthesis of Resin D)
10.4 parts by mass of styrene, 85.3 parts by mass of glycidyl methacrylate, 61.9 parts by mass of monomethacrylate FA-513M (manufactured by Hitachi Kasei Co., Ltd.) having a tricyclodecane skeleton, 43.2 parts by mass of acrylic acid, tetrahydrophthalic anhydride (THPA) Synthesized by the same method as in Synthesis Example 5 except that 19.8 parts by mass was used. The polystyrene-equivalent weight average molecular weight Mw measured by GPC of the resin solution thus obtained was about 8200, and the acid value was 30 mgKOH / g. Propylene glycol monomethyl ether acetate was added to this resin solution so that the solid content became 40% by mass, and the resin D was used.

(Synthesis Example 9: Synthesis of Initiator A)
As the initiator A, 3- (2-acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toroil) -9H- by the method described in International Publication No. 2009/131189. Carbazole was synthesized.

[Preparation of Colored Resin Compositions 1 to 4]
The dyes A to D obtained in the synthetic examples 1 to 4 and the resins A and B obtained in the synthetic examples 5 and 6 are mixed with other components so as to have the composition shown in Table 1 below and colored. Resin compositions 1 to 4 were prepared. At the time of mixing, the mixture was stirred for 1 hour or more until each component was sufficiently mixed, and finally filtered through a 5 μm piece-shaped filter to remove foreign substances.
The upper values in Table 1 represent the content ratio (mass%) of each component to be added in the colored resin composition, and the lower values indicate the content ratio (mass%) of each component in the total solid content. ).

Each compound in Table 1 is as follows.
RS72K: Megafuck RS-72-K, Perfluoroalkyl Group-Containing Polymer, DIC Irganox1010: Pentaerythritol Tetrakiss [3- (3,5-G-tert-butyl-4-hydroxyphenyl) Propinate], BASF JPP -100: Tetraphenyl dipropylene glycol diphosphite, manufactured by Johoku Chemical Industry Co., Ltd. PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[Evaluation of heat resistance]
Each colored resin composition prepared in the above [Preparation of colored resin compositions 1 to 4] is spin-coated on a glass substrate cut into 5 cm squares, and the chromaticity y value after post-baking becomes 0.175. After being applied under reduced pressure and dried under reduced pressure, it was prebaked on a hot plate at 80 ° C. for 3 minutes. Then, after full exposure at an exposure amount of 60 mJ / cm ² , post-baking was performed at 230 ° C. for 30 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity x, y (C light source) and luminance LY in the XYZ color system and the color difference before and after post-baking were measured. ΔE ^* ab was calculated. The results are shown in Table 2.

[Evaluation of light resistance]
Each colored resin composition prepared in the above [Preparation of colored resin compositions 1 to 4] is spin-coated on a glass substrate cut into 5 cm squares, and the chromaticity y value after post-baking becomes 0.175. After being applied under reduced pressure and dried under reduced pressure, it was prebaked on a hot plate at 80 ° C. for 3 minutes. Then, the whole surface was exposed at an exposure amount of 60 mJ / cm ² , and post-baked at 230 ° C. for 30 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticities x and y (C light source) were calculated. Next, it was set on a weatherometer Ci4000 (manufactured by Atlas) via a polarizing plate having a transmittance shown in FIG. 2, and was irradiated with pseudo-sunlight for 20 hours. Then, the spectral transmittance of the film after irradiation was measured in the same manner, and the chromaticity x, y (C light source) was calculated. The color difference (ΔE ^* ab) before and after irradiation was evaluated as light resistance. The results are shown in Table 3.

[Evaluation of solubility of coloring material]
The solubility of the synthesized dyes A to D in propylene glycol monomethylether acetate (manufactured by Daicel Chemical Co., Ltd.) was evaluated by the following procedure.
First, 50 mg of the dye and 450 mg of propylene glycol monomethyl ether acetate were mixed in a 5 mL glass container, stirred for 1 hour, and then allowed to stand at room temperature for 1 hour. The glass container was visually observed and the solubility was evaluated according to the following criteria. The results are shown in Table 4.
○ (Soluble): No residue on the bottom of the container × (Insoluble): Residue on the bottom of the container

[Preparation of colored resin composition for red pixels]
(Synthesis Example 10: Synthesis of Red Pigment 1)
Alcolate was synthesized by reacting 200 parts by mass of t-amyl alcohol with 140 parts by mass of sodium-t-amyl alkoxide at 100 ° C. under a nitrogen atmosphere. This was heated to 60 ° C., a mixed solution of 154 parts by mass of 4-bromobenzonitrile and 88 parts by mass of diisopropyl succinate was added, and the mixture was stirred for 2 hours so that the solution temperature became 85 ° C. or lower. The suspension was further stirred for 15 hours or more, and then added to a mixture of 200 parts by mass of methanol, 1000 parts by mass of water and 50 parts by mass of sulfuric acid cooled to −5 ° C. The mixture was stirred at 0 ° C. for a further 5 hours and then filtered. The solids were washed repeatedly with methanol and water until they were no longer colored. It was dried in a vacuum dryer at 80 ° C. to a constant weight to obtain red pigment 1 (150 parts by mass).

(Synthesis Example 11: Synthesis of Resin E)
A separable flask equipped with a cooling tube was prepared as a reaction vessel, 400 parts by mass of propylene glycol monomethyl ether acetate was charged, and after nitrogen substitution, the temperature of the reaction vessel was raised to 90 ° C. by heating in an oil bath while stirring. bottom.
On the other hand, in the monomer tank, 30 parts by mass of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 60 parts by mass of methacrylic acid, 110 parts by mass of cyclohexyl methacrylate, and t-butylperoxy-2-ethyl. 5.2 parts by mass of hexanoate and 40 parts by mass of propylene glycol monomethyl ether acetate were charged, and 5.2 parts by mass of n-dodecylmercaptan and 27 parts by mass of propylene glycol monomethyl ether acetate were charged in the chain transfer agent tank, and the temperature of the reaction tank was charged. Was stabilized at 90 ° C., and then dropping was started from the monomer tank and the chain transfer agent tank to start the polymerization. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C., and 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts of triethylamine were charged in the reaction vessel, and the mixture was charged as it was at 110 ° C. for 9 hours. It was reacted. After cooling to room temperature, resin E was obtained as a PGMEA solution having a weight average molecular weight Mw of 8000 and an acid value of 101 mgKOH / g.

(Preparation of dye dispersion 1)
9.47 parts by mass of red pigment 1, 2.37 parts by mass of BYK-LPN6919 (manufactured by Big Chemie) as a dispersant, 3.15 parts by mass of resin E in terms of solid content, propylene glycol monomethyl ether acetate. A dye dispersion 1 is prepared by filling a stainless steel container with 60.00 parts by mass (including those derived from a dispersant and resin E) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm and dispersing them with a paint shaker for 6 hours. bottom.

(Preparation of Colored Resin Composition 5)
The dye dispersion liquid 1 containing the red pigment 1, the dye B obtained in the synthetic example 2, and the resins C and D obtained in the synthetic examples 7 and 8 are other components so as to have the compositions shown in Table 5 below. To prepare a colored resin composition 5. At the time of preparation, first, the dye B, the photochromic agent A, and the solvent were thoroughly stirred and dissolved, the dye dispersion 1 was added thereto, and the mixture was stirred for 20 minutes, and then ultrasonically dispersed for 10 minutes to obtain a red liquid. Then, other components were added to the mixture, and the mixture was stirred for 1 hour or more until it was sufficiently mixed, and finally filtered through a 5 μm piece-shaped filter to remove foreign substances.
The upper values in Table 5 represent the content ratio (mass%) of each component to be added in the colored resin composition, and the lower values indicate the content ratio (mass%) of each component in the total solid content. ).

Each compound in Table 5 is as follows.
BYK330: BYK-330, silicon-based surfactant (manufactured by DIC Corporation)
Quenching agent A: Varifast Orange 3209 (manufactured by Orient Chemical Co., Ltd.)

[Evaluation of heat resistance]
The colored resin composition 5 is applied onto a glass substrate cut into 5 cm squares by a spin coating method so that the chromaticity y value after post-baking is 0.326, dried under reduced pressure, and then placed on a hot plate. It was prebaked at 80 ° C. for 3 minutes. Then, after full exposure at an exposure amount of 40 mJ / cm ² , post-baking was performed at 230 ° C. for 20 minutes in a clean oven. The spectral transmittance of the obtained film was measured with a spectrophotometer U-3310 (manufactured by Hitachi, Ltd.), and the chromaticity x, y (C light source) and luminance LY in the XYZ color system and the color difference before and after post-baking were measured. ΔE ^* ab was calculated. The results are shown in Table 6.

[Evaluation of contrast]
Contrast measuring device (Contrast Tester CT-1 (manufactured by Tsubosaka Electric Co., Ltd.), with the film surface of the colored resin composition 5 obtained in the above [evaluation of heat resistance] after post-baking facing down. It was installed in a BM-5AS (manufactured by Topcon, a luminance meter) and an F-10 light source (with a polarizing plate inserted), and the contrast was measured with a blank value of 18,000. The results are shown in Table 6.

[Evaluation of light resistance]
The post-baked film of the colored resin composition 5 obtained in the above [evaluation of heat resistance] was set on the weatherometer Ci4000 (manufactured by Atlas) via the polarizing plate having the transmittance shown in FIG. , Pseudo-sunlight was irradiated for 40 hours. Then, the spectral transmittance of the film after irradiation was measured in the same manner as in the above-mentioned [evaluation of heat resistance], and the chromaticity x, y (C light source) was calculated. The color difference (ΔE ^* ab) before and after irradiation was evaluated as light resistance, and the results are shown in Table 6.

As is clear from Tables 2, 4 and 6, the colored resin compositions of Examples 1 to 5 contain a dye that is sufficiently soluble in a solvent and are excellent in brightness.

Although the detailed mechanism regarding the effect of the present invention has not been clarified, it is considered as follows.
The colored resin compositions of Examples 1 to 5 contain the xanthene dye represented by the general formula (I), but the number of atoms constituting the main chain in X ¹ and X ² is 4 or more. This facilitates twisting and rotational movement of the side chain, and the fact that one or more of the methylene groups constituting the alkylene group in X ¹ and X ² are replaced by polar groups makes it compatible with the solvent. It is considered that the sex is higher and the solubility is higher.

In particular, the colored resin composition for red pixels of Example 5 exhibits extremely high luminance in red pixel applications. Since the transmittance of the xanthene dye has a high transmittance in the vicinity of 560 to 650 nm as compared with the transmission spectrum of red pigments such as diketopyrrolopyrrole pigments and anthraquinone pigments, it is red in combination with these pigments. It is considered that a red pixel having higher brightness can be obtained by creating the pixel. Further, in order to improve the luminance, a spectral shape that transmits wavelengths in the vicinity of 560 to 650 nm as much as possible and absorbs wavelengths less than 560 nm as much as possible is preferable, and a rectangular spectrum is ideal. If the colorant is highly soluble, it dissolves at the molecular level and the absorbance increases, so it is considered that the spectrum is closer to a rectangular spectrum and the brightness is increased.

On the other hand, as is clear from Tables 3 and 6, the colored resin compositions of Examples 1 to 5 are excellent in light resistance. Although the detailed mechanism has not been clarified, the π-π interaction and hydrophobicity of the benzene ring bonded to X ¹ and X ² by including the xanthene dye represented by the general formula (I). It is considered that the interaction facilitates stacking between molecules and causes deactivation of the excited state, resulting in high light resistance.

100 Organic EL element 10 Transparent support substrate 20 pixels 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (7)

A colored resin composition containing (A) a coloring material, (B) a solvent, and (C) a binder resin.
A colored resin composition, wherein the coloring material (A) contains a xanthene dye represented by the following general formula (I).

(In the above formula (I), R ¹ to R ⁶ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k independently represent an integer of 0 to 5, and l and m each independently represent an integer of 0 to 3.
X ¹ and X ² each represent an alkylene group which may independently have a substituent, and one or more of the methylene groups constituting the alkylene group are from -O- , -CO-, and -NR ^7- . It is replaced by at least one selected from the group (however, among the above-mentioned alkylene groups, alkanes are replaced.
Except for those in which the methylene group constituting the len group is replaced with -S-) . However, the number of atoms constituting the main chain of X ¹ and X ² is 4 or more.
R ⁷ represents a hydrogen atom or an alkyl group which may have a substituent. ) The colored resin composition according to claim 1, wherein the coloring material (A) further contains a red pigment. The colored resin composition according to claim 1 or 2, further containing (D) a polymerizable monomer. Claim 1 further contains (E) a photopolymerization initiation component and / or (E') a thermal polymerization initiation component.
The colored resin composition according to any one of 3 to 3. The colored resin composition according to any one of claims 1 to 4, further comprising an antioxidant. A color filter having pixels formed by using the colored resin composition according to any one of claims 1 to 5. An image display device having the color filter according to claim 6.

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