JP2019159169A - Coloring resin composition, color filter and image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored resin composition containing a dye sufficiently soluble in a solvent and having excellent brightness. A colored resin composition containing (A) a coloring material, (B) a solvent and (C) a binder resin, wherein the (A) coloring material has a nitrogen atom having a phenyl group at the 2nd and 8th positions. A colored resin composition comprising, and containing a xanthene dye having a phenyl group having a sulfonic acid group at the 5-position. [Selection diagram] None

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 display devices and organic EL (Electroluminescence) display devices are widely used, and color filters are used for these displays. With the trend of energy saving, color filters are required to have higher color purity, higher brightness, and higher contrast.
Until now, colored resin compositions using pigments have been mainly used as color filter forming materials, but in order to obtain high brightness and high contrast, for example, Non-Patent Document 1 specifies the particle size of pigment particles. A method of finely dispersing the color to a half or less of the coloration wavelength is disclosed.

  On the other hand, a dye has been developed as a coloring material used in a colored resin composition for a color filter. For example, Patent Document 1 discloses a colored resin composition for a color filter including a specific color material and a blue color material.

JP 2014-153570 A

Kiyoshi Hashizume, “Color Material Association”, December 1967, p608

Conventionally, the transmittance peak of blue pixels among red, green and blue is relatively low, and it is necessary to improve the overall luminance while maintaining the balance during white display. Vigorous studies have been made on the dyeing of blue pixels. On the other hand, in recent years, the trend toward higher brightness from the viewpoint of power consumption has led to a demand for dyeing the red pixels of the color filter.
As a result of studies 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 luminance. It has been found that it is necessary to use dyes.
The colored resin composition described in Patent Document 1 is intended for a blue pixel application, and no examination is made for a red pixel application. Further, as a result of the study by the present inventors, it has been found that the dye described in Patent Document 1 does not have sufficient luminance in practical use for red pixels.

  Then, this invention is made | formed in view of the subject of the said prior art, and makes it a subject to provide the coloring resin composition excellent in the brightness | luminance which contains the dye fully melt | dissolved in a solvent.

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

[1] A colored resin composition containing (A) a color material, (B) a solvent, and (C) a binder resin,
The colored resin composition, wherein the color 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 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k each independently represents an integer of 0 to 5, and l and m each independently represents an integer of 0 to 3.
X ¹ and X ² each independently represents an alkylene group which may have a substituent, and one or more of methylene groups constituting the alkylene group are —O—, —S—, —CO—, and — NR ⁷ - and substituted with at least one selected from the group consisting of. 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 color material (A) further contains a red pigment.
[3] The colored resin composition according to [1] or [2], further comprising (D) a polymerizable monomer.
[4] The colored resin composition according to any one of [1] to [3], further comprising (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 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].

  ADVANTAGE OF THE INVENTION According to this invention, the coloring resin composition excellent in the brightness | luminance which contains the dye fully melt | dissolved in a solvent can be provided.

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

Embodiments of the present invention will be described in detail below, 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) acryl”, “(meth) acrylate” and the like mean “at least one of acrylic and methacryl”, “at least one of acrylate and methacrylate”, and the like, for example, “( “Meth) acrylic acid” means “at least one of acrylic acid and methacrylic acid”.

The “total solid content” means all components of the colored resin composition of the present invention other than the solvent component.
Furthermore, “aromatic ring” means both “aromatic hydrocarbon ring” and “aromatic heterocycle”.
A term such as “CI Pigment Green” means a color material name included in the color index (CI).

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

[(A) Color material]
(Xanthene dye represented by the general formula (I))
The color material (A) contained in the colored resin composition of the present invention contains a xanthene dye represented by the following general formula (I) (hereinafter sometimes referred to as “xanthene dye (I)”). To do.

In the above formula (I), R ^{1 to} R ⁶ each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k each independently represents an integer of 0 to 5, and l and m each independently represents an integer of 0 to 3.
X ¹ and X ² each independently represents an alkylene group which may have a substituent, and one or more of methylene groups constituting the alkylene group are —O—, —S—, —CO—, and — NR ⁷ - and substituted with at least one selected from the group consisting of. 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 4 or more atoms constituting the main chain of X ¹ and X ² , so that twisting of the bond and rotational movement are facilitated, and X ¹ And the methylene group constituting the alkylene group in X ² is replaced with a polar group, it is considered that the affinity with the solvent is increased and the solubility is increased. Thereby, the transmittance at 560 to 650 nm is high, the transmittance at less than 560 nm is low, and a rectangular transmission spectrum is obtained, and it is considered that the luminance for red pixel use becomes 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 of the bond and the rotational movement are facilitated, so that no radiation is caused by internal conversion or vibration relaxation even when photoexcitation occurs. It is thought that it is easy to deactivate and light resistance is also improved. Further, it is considered that the benzene ring bonded to X ¹ and X ² is likely to be stacked by π-π interaction or hydrophobic interaction between molecules, and it is easy to cause deactivation of an excited state, thereby improving light resistance.

(X ¹ and X ²⁾
In the formula (I), X ¹ and X ² each independently represent an alkylene group which may have a substituent, and one or more methylene groups constituting the alkylene group are —O—, —S—. , —CO—, and —NR ⁷ — are replaced with 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.

Examples of the alkylene group for X ¹ and X ² include a linear alkylene group, a branched alkylene group, a cyclic alkylene group, or a group in which these are bonded. The alkylene group is preferable.
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, still more preferably 10 or less, and particularly preferably 7 or less. There exists a tendency for a solubility to improve by making it into the said lower limit or more, and there exists a tendency for a synthesis | combination to become easy by making it into the said upper limit or less.

  Specific examples of the alkylene group include a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group. From the viewpoints of solubility and ease of synthesis, a pentylene group is preferable.

One or more methylene groups constituting the alkylene group of X ¹ and X ² are replaced with 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 methylene groups constituting the alkylene group may be replaced with one selected from the group consisting of —O—, —S—, —CO—, and —NR ⁷ —. One or more of the constituting methylene groups may be replaced by a combination of two or more selected from the group consisting of —O—, —S—, —CO—, and —NR ⁷ —. As a combination of two or more, -O-CO -, - CO -O -, - such as CO-NR ⁷ and the like.

Any methylene group constituting the alkylene group may be replaced with the aforementioned group. From the viewpoint of ease of synthesis, the methylene group adjacent to the benzene ring in formula (I) is replaced with the aforementioned group. Replacement is preferred.
The number of atoms constituting the main chain of X ¹ and X ² is 4 or more, but 5 or more is preferable, 15 or less is preferable, 12 or less is more preferable, 10 or less is more preferable, and 7 or less is particularly preferable. There exists a tendency for a solubility to improve by making it into the said lower limit or more, and there exists a tendency for a synthesis | combination to become easy by making it into the said upper limit or less.

X ¹ and X ² are preferably divalent groups represented by the following general formula (I-1) 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 alkylene group, a cyclic alkylene group, and a group obtained by bonding these, 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, preferably 4 or more, more preferably 5 or more, 14 or less, more preferably 11 or less, still more preferably 9 or less, and even more preferably 7 or less. The following are particularly preferred: There exists a tendency for solubility to improve more by setting it as the said lower limit or more, and there exists a tendency for a synthesis | combination to become easy by setting it as the said upper limit or less.

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

(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 —. One type selected from the group consisting of —O—, —S—, —CO—, and —NR ⁷ — may be used, or a combination of two or more types may be used. As a combination of two or more, -O-CO -, - CO -O -, - such as CO-NR ⁷ and the like.

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

(R ¹ ~R ⁶⁾
In the formula (I), R ^{1 to} R ⁶ each independently represents 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 for R ^{1 to} R ⁶ include a linear, branched, or cyclic alkyl group. The number of carbon atoms 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, and still more preferably 5 or less. When the amount is not less than the lower limit, heat resistance tends to be improved, and when the amount is not more than the upper limit, synthesis is easy, and crystallization is easy and purification tends to be 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, 3- A methylbutyl group etc. are mentioned. Among these, a methyl group, an ethyl group, and an n-propyl group are preferable from the viewpoint of ease 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, and is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. When the amount is not less than the lower limit, heat resistance tends to be improved, and when the amount is not more than the upper limit, synthesis is easy, and crystallization is easy and purification tends to be 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. An oxy group, 3-methylbutyloxy group, etc. are mentioned. 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, and an iodine atom. Among these, a fluorine atom, a chlorine atom, and a bromine atom are preferable from the viewpoint of ease of synthesis and solubility, and a chlorine atom is more preferable.

Among these, R ¹ and R ² are preferably an alkyl group which may have a substituent or a halogen atom, and more preferably a halogen atom, from the viewpoint of ease of synthesis and crystallinity.

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

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

(H to k)
In the formula (I), h to k each independently represents 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, and still more preferably 2 or less. There exists a tendency for solubility to improve by setting it as the said lower limit or more, and there exists a tendency which it becomes easy to synthesize | combine by setting it as the said upper limit or less.
When h and i are 1 or more, the substitution position is not particularly limited, but 2-position and 4-position are preferred, and 4-position is more preferred.

On the other hand, j and k are each independently preferably 1 or more, more preferably 2 or more, and preferably 4 or less, more preferably 3 or less. The absorption peak becomes longer in wavelength by setting it to the lower limit value or more, and the luminance tends to be improved by increasing the molar extinction coefficient, and the absorption peak becomes too long wavelength by setting it to the upper limit value or less. There is a tendency to suppress a decrease in luminance.
When j and k are 1 or more, the substitution position is not particularly limited, but 2-position, 4-position and 6-position are preferable, and 2-position and 6-position are more preferable.

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

  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 first position and the second position is the clockwise adjacent position, the second position and the sixth position are The 2nd position is preferable.

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

(Substituent group W1)
Fluorine atom, chlorine atom, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy group, alkyl having 2 to 9 carbon atoms Carbonyloxy group, sulfamoyl group, alkylsulfamoyl group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 9 carbon atoms, phenethyl group, hydroxyethyl group, acetylamide group, and alkyl group having 1 to 4 carbon atoms 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, preferred are an alkoxyl group having 1 to 8 carbon atoms, a cyano group, an acetyloxy group, an alkyl carboxyl group having 2 to 8 carbon atoms, a sulfamoyl group, an alkylsulfamoyl group having 2 to 9 carbon atoms, and a fluorine atom. .

  Moreover, although the presence form of the xanthene dye represented by the formula (I) in the colored resin composition is not particularly limited, 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 more 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 most the upper limit value, synthesis tends to be easy.

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

(Synthesis Method of Xanthene Dye Represented by Formula (I))
The xanthene dye of the present invention can also be synthesized with reference to JP2013-253168A, using a commercially available xanthene dye (for example, "DCSF" manufactured by Chugai Kasei Co., Ltd.) as a starting material.

(Content ratio of xanthene dye represented by formula (I))
The color material (A) in the colored resin composition of the present invention may contain one type of xanthene dye represented by the formula (I) or two or more types.
The content ratio of the color 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 more preferably 30% by mass or more. Is more preferably 35% by mass or more, most preferably 38% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, further preferably 60% by mass or less, and 50% by mass or less. Is particularly preferred. By setting it to the lower limit value or more, there is a tendency that desired color characteristics are easily obtained, and by setting the upper limit value or less, the photosensitivity tends to be improved.

  In addition, the content ratio of the xanthene dye represented by the formula (I) in the color material (A) is not particularly limited, but is preferably 5% by mass or more, and 10% by mass or more based on the color material (A). 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, the luminance tends to be improved, and when it is at most the upper limit, the durability tends to be good.

(Other color materials)
The (A) color material in the colored resin composition of the present invention may contain other color 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 material 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, and further preferably 20% by mass or more in the total solid content. 25 mass% or more is especially preferable, 70 mass% or less is preferable, 60 mass% or less is more preferable, 50 mass% or less is further more preferable, and 40 mass% or less is especially preferable. Further, the content ratio of the other color material in the color material (A) 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. Preferably, 90 mass% or less is preferable, 85 mass% or less is more preferable, 80 mass% or less is further more preferable, and 75 mass% or less is particularly preferable. When it is at least the lower limit, durability and color characteristics tend to be compatible, and when it is at most the upper limit, the photosensitivity tends to be improved.

(Other dyes)
Other dyes include, for example, azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, cyanine dyes, triarylmethane dyes, Preferred examples include dipyrromethene dyes and xanthene dyes.

  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. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes 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 etc. are mentioned.

  Other examples of the phthalocyanine dye include C.I. I. Direct Blue 86, C.I. I. Direct Blue 199, C.I. I. Vat Blue 5, those described in JP-A No. 2002-14222, JP-A No. 2005-134759, JP-A No. 2010-191358 and JP-A No. 2011-148950 are examples of quinoneimine dyes such as C . I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

Examples of triarylmethane dyes include C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, and the like.
Furthermore, examples of the cyanine dye include those described in International Publication No. 2011/162217, and the preferred embodiments are also the same.

  Examples of dipyrromethene dyes include, for example, JP-A-2008-292970, JP-A-2010-84009, JP-A-2010-84141, JP-A-2010-85454, JP-A-2011-158654, and JP-A-2011-158654. Examples described in JP 2012-158739 A, JP 2012-224852 A, JP 2012-224849 A, JP 2012-224847 A, JP 2012-224846 A, and the like can be given.

Examples of xanthene dyes 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 Dye” (Horiguchi Hiroshi, Sankyo Publishing, 1968), pages 326 to 348, etc. Is mentioned.
In particular, when a red pixel is formed, a xanthene dye is preferable from the viewpoint of luminance and heat resistance.
In the colored resin composition of the present invention, only one kind of other dye may be contained, or two or more kinds thereof may be contained.

(Pigment)
For example, when forming a red pixel of a color filter, pigments of various colors such as red and yellow can be used as the pigment.
Examples of the chemical structure of the pigment include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, and perylene. In addition, various inorganic pigments can be used. Hereinafter, specific examples of usable pigments are indicated by pigment numbers.

  Examples of red pigments 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, 17 , 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 luminance, C.I. I. Pigment red 177, 254, or 275, and more preferably C.I. I. Pigment Red 177 or 254. Moreover, it is preferable to use the diketopyrrolopyrrole pigment represented by Formula (P) described in Unexamined-Japanese-Patent No. 2013-014750 from a viewpoint of contrast. These may be used alone or in a combination of two or more in any combination and ratio.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, and the like. Among these, from the viewpoint of luminance, C.I. I. Pigment Yellow 129, 138, 139, 150 or 185, more preferably C.I. I. Pigment Yellow 138, 150 or 185.
These may be used alone or in a combination of two or more 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 a pixel with high contrast, and specifically, the average primary particle size is 40 nm or less. Is preferable, and it is more preferable that it is 35 nm or less.
Here, the average primary particle diameter 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 a primary particle image of the pigment is obtained by observation with a transmission electron microscope (TEM). From this image, the particle size of each pigment particle is determined for a plurality of (usually about 200 to 300) pigment particles, with the diameter corresponding to the area circle converted to the diameter of a circle having the same area.
Using the obtained primary particle size value, the number average value is calculated according to the following formula 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 colorants, it is preferable to include other pigments from the viewpoint of improving heat resistance and light resistance. In particular, when a red pixel is formed, a red pigment is preferably included from the viewpoint of chromaticity, luminance, and contrast. I. Pigment red 177, C.I. I. Diketopyrrolopyrrole pigments represented by the formula (P) described in CI Pigment Red 254 and JP2013-014750A are more preferable.

[(B) Solvent]
The solvent (B) contained in the colored resin composition of the present invention has a function of adjusting the viscosity by dissolving or dispersing each component contained in the colored resin composition.
(B) As a solvent, what is necessary is just to be able to melt | dissolve or disperse | distribute each component which comprises a colored resin composition, and it is preferable to select a thing whose boiling point is the range of 100-200 degreeC. More preferably, it has a boiling point of 120-170 ° C.

Examples of such solvents 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-mono t-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;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
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 Glycol alkyl 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, diamyl ether, ethyl isobutyl 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;
Mono- 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;
Cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;

Aromatic hydrocarbons such as benzene, toluene, xylene, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, cyclohexyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyric acid Methyl, ethyl caprylate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3- Linear or cyclic esters such as butyl methoxypropionate, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Ether ketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile:
These solvents may be used alone or in combination of two or more.

In the above solvent, it is preferable to contain glycol monoalkyl ethers from the viewpoint of adhesion between the substrate and the coating film, and the coating film can form a uniform film thickness. Among these, propylene glycol monomethyl ether is particularly preferable from the viewpoint of solubility of various components in the colored resin composition.
Further, for example, when the above-mentioned other pigments are included as optional components, the balance of coating properties, surface tension, etc. is good, and glycols are further used as solvents from the viewpoint of relatively high solubility of the constituent components in the colored resin composition. It is more preferable to use a mixture of alkyl ether acetates. In addition, in colored resin compositions containing pigments, glycol monoalkyl ethers are highly polar and tend to aggregate the pigment, which may reduce storage stability, such as increasing the viscosity of the colored resin composition. For this reason, it is preferable that the amount of glycol monoalkyl ethers used is not excessively large, and the proportion of 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 a slit coat method corresponding to a recent large substrate or the like, it is also preferable to use a solvent having a boiling point of 150 ° C. or higher. In this case, the content of the 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 total amount of the solvent (B). If the amount of the high boiling point solvent is too small, for example, a dye component may precipitate and solidify at the tip of the slit nozzle to cause foreign matter defects, and if it is too large, the drying speed of the composition will be slowed down. There is a concern that the filter manufacturing process may cause problems such as tact defects in the vacuum drying process and pin marks of prebaking.

The solvent having a boiling point of 150 ° C. or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, a solvent having a boiling point of 150 ° C. or higher may not be included separately. .
The colored resin composition of the present invention may be used for color filter production by the ink jet method, but in color filter production by the ink jet method, the ink emitted from the nozzle is very small, from several to several tens pL, There is a tendency for the solvent to evaporate and the ink to concentrate and dry before landing on the periphery of the nozzle opening or in the pixel bank. In order to avoid this, it is preferable that the solvent has a high boiling point. 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 220 ° C. or higher. Moreover, it is preferable that the high boiling point solvent whose boiling point is 180 degreeC or more is 50 mass% or more in (B) solvent. By setting it to the lower limit value or more, the effect of preventing evaporation of the solvent from the ink droplets tends to be sufficiently exerted.

  The content of the solvent in the entire colored resin composition of the present invention is not particularly limited, but the upper limit is usually 99% by mass or less, preferably 90% by mass or less, more preferably 80% by mass or less. 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 (C) binder resin is not limited in any way as long as it is soluble in the above-mentioned solvent and can form a cured film having a sufficient degree of curing. From the viewpoint of formation, 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, Although the high molecular compound described in each gazette etc., such as Unexamined-Japanese-Patent No. 2003-233179, can be used, Preferably the following (C-1)-(C-5) resin etc. are mentioned especially.

(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. Resin to be added, or 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 hydroxyl group generated by the addition reaction. .)
(C-2): Carboxyl group-containing linear alkali-soluble resin (C-2) (hereinafter sometimes 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 sometimes referred to as “resin (C-3)”).
(C-4): (Meth) acrylic resin (hereinafter sometimes referred to as “resin (C-4)”)
(C-5): Epoxy acrylate resin having a carboxyl group (hereinafter sometimes referred to as “resin (C-5)”)
Of these, the resin (C-1) is particularly preferable, and the resin will be described below.

The resins (C-2) to (C-5) may be anything as long as they are dissolved in an alkaline developer and are soluble to the extent that the desired development processing is performed. It is the same as that described as the same item of 2009-025813 gazette. The preferred embodiment is also the same.
(C-1): With respect to a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, an unsaturated monobasic acid is added to at least a part of the epoxy group of the copolymer. As one of 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 hydroxyl group generated by the addition reaction, or an epoxy group, Unsaturated in 10 to 100 mol% of the epoxy group of the copolymer with respect to the copolymer of 5 to 90 mol% of (meth) acrylate and 10 to 95 mol% of other radical polymerizable monomer 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 a hydroxyl group 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 (meta). ) Acrylate glycidyl ether and the like. Of these, glycidyl (meth) acrylate is preferred. These epoxy group-containing (meth) acrylates may be used alone or in combination of two or more.

  The other radical polymerizable monomer copolymerized with the epoxy group-containing (meth) acrylate is not particularly limited as long as the effects of the present invention are not impaired. For example, vinyl aromatics, dienes, (meth) Examples include acrylic acid esters, (meth) acrylic acid amides, vinyl compounds, unsaturated dicarboxylic acid diesters, monomaleimides, and the like, and in particular, mono (meth) having a structure represented by the following formula (III) Acrylate 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% among the repeating units derived from “other radical polymerizable monomers”. The content is preferably 10 to 70 mol%, more 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 formula (IV), R ^{91 to} R ⁹⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ⁹⁶ and R ⁹⁸ may be connected to each other to form a ring.
The ring formed by connecting R ⁹⁶ and R ⁹⁸ is preferably an aliphatic ring, may be saturated or unsaturated, and preferably has 5 to 6 carbon atoms.
Among these, as the structure represented by the formula (IV), a structure represented by the following structural formula (IVa), (IVb), or (IVc) is particularly preferable.

In addition, the mono (meth) acrylate which has a structure represented by said Formula (IV) may be used individually by 1 type, and may use 2 or more types together.
“Other radical polymerizable monomers” other than the mono (meth) acrylate having the structure represented by the formula (IV) can improve heat resistance and strength excellent in the colored resin composition. , Styrene, (n-butyl) (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, benzyl (meth) acrylate , (Meth) acrylic acid-2-hydroxyethyl, N-phenylmaleimide, N-cyclohexylmaleimide.

The content of the repeating unit derived from at least one selected from the above 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 radical polymerizable monomer.
In the present invention, as a copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer, 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth) acrylate, and others Is preferably composed of 10 to 95 mol% of repeating units derived from the radically polymerizable monomer, more preferably composed of 20 to 80 mol% of the former and 80 to 20 mol% of the latter. What consists of 70 mol% and the latter 70-30 mol% is especially preferable.

Within the above range, the addition amount of the polymerizable component and alkali-soluble component described later is sufficient, and the heat resistance and the strength of the film are sufficient, which is preferable.
The epoxy group portion of the epoxy group-containing copolymer synthesized as described above is reacted with an unsaturated monobasic acid (polymerizable component) and a polybasic acid anhydride (alkali-soluble component).
Here, as an unsaturated monobasic acid added to an epoxy group, a well-known thing can be used, For example, unsaturated carboxylic acid which has an ethylenically unsaturated double bond is mentioned.

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

By adding such components, polymerizability can be imparted to the binder resin used in the present invention.
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%. It is preferable for it to be in the above range since the colored resin composition is excellent in stability over time. In addition, a well-known method is employable as a method of adding unsaturated monobasic acid to the epoxy group of a copolymer.

Furthermore, a well-known thing can be used as a polybasic acid anhydride added to the hydroxyl group produced when an unsaturated monobasic acid is added to the epoxy group of a 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 anhydrides of three or more bases such as tetracarboxylic acid anhydride and biphenyltetracarboxylic acid anhydride. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferred. These polybasic acid anhydrides may be used individually by 1 type, and may use 2 or more types together.

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 group generated by adding an unsaturated monobasic acid to the epoxy group of the copolymer, preferably 20 to 90 mol. %, More preferably 30 to 80 mol%.

Within the above range, the remaining film ratio and solubility during development are sufficient, which is preferable.
In addition, a well-known method is employable as a method of adding a polybasic acid anhydride to the said hydroxyl group.
Furthermore, in order to improve photosensitivity, after adding the above-mentioned polybasic acid anhydride, glycidyl (meth) acrylate or a glycidyl ether compound having a polymerizable unsaturated group is added to a part of the generated carboxyl group. May be. Such a resin structure is described in, for example, Japanese Patent Application Laid-Open Nos. 8-297366 and 2001-89533.

The above-mentioned binder resin (C) has a polystyrene equivalent weight average molecular weight (Mw) measured by GPC (gel permeation chromatography), preferably 3000 or more, more preferably 5000 or more, and preferably 100,000 or less, 50,000. The following is more preferable, 30000 or less is more preferable, and 10,000 or less is particularly preferable. Within the above range, heat resistance, film strength, and solubility in a developer are preferable.
Moreover, as a standard of molecular weight distribution, the ratio of weight average molecular weight (Mw) / number average molecular weight (Mn) is preferably 2.0 to 5.0.

  In addition, 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 more preferable. When the amount is not less than the lower limit, the solubility in the developer tends to be good, and when the amount is not more than the upper limit, 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 preferably 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the value is not less than the lower limit value, a film thickness suitable for pattern formation by development tends to be ensured, and when the value is not more than the upper limit value, 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. (D) The polymerizable monomer is not particularly limited as long as it is a polymerizable low-molecular compound, but it may be an addition-polymerizable compound having at least one ethylenic double bond (hereinafter referred to as “ethylenic compound”). Preferably).
The ethylenic compound is a compound having an ethylenic double bond that undergoes addition polymerization and cures by the action of a photopolymerization initiation component described later when the colored resin composition of the present invention is irradiated with actinic rays. In addition, the (D) polymerizable monomer in this invention means the concept opposite to what is called a polymeric substance, and also includes a dimer, a trimer, and an oligomer other than a monomer 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 that the polyfunctional ethylenic monomer has 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, it is 10 or less. By setting it as the said lower limit or more, there exists a tendency for polymerizability to improve and to become high sensitivity, and there exists a tendency for developability to become more favorable by setting it as the said upper limit or less.

  (D) Examples of the ethylenic compound in the 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 of aromatic polyhydroxy compounds and unsaturated carboxylic acids; Esterification of unsaturated carboxylic acids with polyvalent carboxylic acids and polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds described above An ester obtained by the reaction; an ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound;

  Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (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 include (meth) acrylic acid esters such as acrylate and glycerol (meth) acrylate. In addition, the (meth) acrylic acid portion of these (meth) acrylic acid esters is replaced with an itaconic acid portion, a crotonic acid portion replaced with a crotonic acid portion, or a maleic acid ester replaced with a maleic acid portion, etc. Is mentioned.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone di (meth) acrylate, resorcin di (meth) acrylate, pyrogallol tri (meth) acrylate, and the like.
The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound may be a single substance or a mixture. Representative examples are condensates of (meth) acrylic acid, phthalic acid, and ethylene glycol; condensates of (meth) acrylic acid, maleic acid, and diethylene glycol; condensation of (meth) acrylic acid, terephthalic acid, and pentaerythritol A condensate of (meth) acrylic acid, adipic acid, butanediol, and glycerin.

  Examples of the ethylenic compound having a urethane skeleton obtained by reacting a polyisocyanate compound and a (meth) acryloyl group-containing hydroxy compound include aliphatic diisocyanates such as hexamethylene diisocyanate and trimethylhexamethylene diisocyanate; alicyclic rings such as cyclohexane diisocyanate and isophorone diisocyanate. Formula diisocyanates; 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 A reaction product with a group-containing hydroxy compound is exemplified.

In addition, examples of the ethylenic compound used in the present invention include (meth) acrylamides such as ethylene bis (meth) acrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. .
Among these, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids are preferred, pentaerythritol or (meth) acrylic acid esters of dipentaerythritol are more preferred, and dipentaerythritol hexa (meth) acrylate is particularly preferred.

  The ethylenic compound may be a monomer having an acid value. The monomer having an acid value is, for example, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having a group is preferable, and in this ester, the aliphatic polyhydroxy compound is at least one of pentaerythritol and dipentaerythritol.

These monomers may be used alone, but since it is difficult to obtain a single compound in production, a mixture of two or more kinds may be used.
Moreover, you may use together the polyfunctional monomer which does not have an acid group, and the polyfunctional monomer which has an acid group as (D) polymeric monomer as needed.
A preferable acid value of the polyfunctional monomer having an acid group is 0.1 to 100 mg-KOH / g, and particularly preferably 5 to 80 mg-KOH / g.

When it is within the above range, the development and dissolution characteristics are hardly deteriorated, and the production and handling are easy. Furthermore, it is preferable because the photopolymerization performance is hardly lowered and the curability such as the surface smoothness of the pixel is good.
In the present invention, a more preferred polyfunctional monomer having an acid group is, for example, a mixture containing succinic acid ester of dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate as a main component. It is also possible to use this polyfunctional monomer in combination with another polyfunctional monomer.

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, and more preferably 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 (D) polymerizable monomer to 100 parts by mass of (A) colorant is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 30 parts by mass or more. More preferably, it is 40 parts by mass or more, particularly preferably 45 parts by mass or more, and is usually 500 parts by mass or less, preferably 200 parts by mass or less, more preferably 100 parts by mass or less.
Within the above range, photocuring is appropriate, poor adhesion during development is difficult to place, the cross-section after development is difficult to reverse taper, and further, peeling phenomenon and omission failure due to lower solubility are difficult to place. preferable.

[(E) photopolymerization initiating component and (E ′) thermal polymerization initiating component]
The colored resin composition of the present invention preferably contains at least one of (E) photopolymerization initiation component and (E ′) 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 includes a resin having an ethylenic double bond as the component (C), or includes an ethylenic compound as the component (D), it directly absorbs light, or It is preferable to contain at least one of a photopolymerization initiating component that has a function of generating a polymerization active radical and a thermal polymerization initiating component that generates a polymerization active radical by heat by causing a photosensitization to cause a decomposition reaction or a hydrogen abstraction reaction. . In the present invention, the component (E) as a photopolymerization initiation component refers to a photopolymerization initiator (hereinafter also referred to as “(E1) component”), a polymerization accelerator (hereinafter, optionally referred to as “(E2) component”). ")" And a sensitizing dye (hereinafter also referred to as "(E3) component").

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

  Examples of (E1) photopolymerization initiator constituting the photopolymerization initiating component include titanocene derivatives described in, for example, JP-A Nos. 59-152396 and 61-151197; JP-A-10-300922 Hexaarylbiimidazole derivatives described in JP-A-11-174224, JP-A-2000-56118, etc .; halomethylated oxadiazole derivatives described in JP-A-10-39503, etc., halomethyl- 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; oxime ester derivatives described in JP 2000-80068 A and the like .

Specific examples include photopolymerization initiators described in International Publication No. 2009/107734.
Among these photopolymerization initiators, α-aminoalkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, acetophenone derivatives, and thioxanthone derivatives are more preferable.
Further, examples of oxime ester derivatives include 2- (benzoyloxyimino) -1- [4- (phenylthio) phenyl] -1-octanone, O-acetyl-1- [6- (2-methylbenzoyl) -9. -Ethyl-9H-carbazol-3-yl] ethanone oxime and a compound represented by the following formula (V).

(In formula (V), R ¹⁰¹ represents 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. An alkyl group, any of which may have a substituent, or R ¹⁰¹ may be bonded to X or Z to form a ring;
R ¹⁰² is an alkanoyl group having 2 to 20 carbon atoms, alkenoyl of 3 to 25 carbon atoms, cycloalkanoyl group having 4 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, 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 heteroaryloyl group having 3 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms, It may have a substituent.

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

In formula (VI), R ¹⁰¹ , R ¹⁰² and Z have the same definitions as in formula (V). R ^{103 to} R ¹⁰⁹ each independently represent a hydrogen atom or an arbitrary substituent.

In 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 represents 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 having 4 to 25 carbon atoms. Indicates a 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 having 1 to 4 carbon atoms. Za represents ^a phenyl group which may be substituted with an alkyl group or a naphthyl group which may be substituted with a morpholino group.

  Commercial products may be used as the oxime initiator. Examples of commercially available products are OXE-01, OXE-02 (BASF), TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-314 (Changzhou Powerful Electronic New Materials Co., Ltd.) Ltd. (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD).

  Other photopolymerization initiators include benzoin alkyl ethers, anthraquinone derivatives; acetophenone derivatives such as 2-methyl- (4′-methylthiophenyl) -2-morpholino-1-propanone, 2-ethylthioxanthone, 2 Thioxanthone derivatives such as 1,4-diethylthioxanthone, benzoic acid ester derivatives, acridine derivatives, phenazine derivatives, anthrone derivatives and the like. Commercial 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, LUCIRAC8, IRGACURE8, 19 Is a registered trademark).

Among these photopolymerization initiators, α-aminoalkylphenone derivatives, thioxanthone derivatives, and oxime ester derivatives are more preferable. In particular, oxime ester derivatives are preferable.
Examples of the (E2) polymerization accelerator used as necessary 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 heterocyclic ring such as benzoxazole and 2-mercaptobenzimidazole; mercapto compounds such as aliphatic polyfunctional mercapto compounds.

Each of these (E1) photopolymerization initiator and (E2) polymerization accelerator may be used alone or in combination of two or more.
Further, (E3) sensitizing dye is used for the purpose of increasing the sensitivity as required. A suitable sensitizing dye is used depending on the wavelength of the image exposure light source. For example, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756; No. 239703, JP-A-5-289335, etc., a coumarin dye having a heterocyclic ring; JP-A-3-239703, JP-A-5-289335, etc .; 3-ketocoumarin dye; Pyrromethene dyes described in JP-A-6-19240 and the like; JP-A 47-2528, JP-A 54-155292, JP-B 45-37377, JP-A 48-84183, JP JP 52-112681, JP 58-15503, JP 60-88005, JP 59-56403, JP 2-69, HirakiAkira 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, JP-dyes having a dialkyl aminobenzene skeleton described in JP-A-4-288818 discloses the like.
(E3) A 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, 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, more Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it is 5 mass% or less. There exists a tendency which can suppress the fall of the sensitivity with respect to exposure light by setting it as the said lower limit or more, and the tendency which can suppress the development defect accompanying with the fall of the solubility with respect to the developing solution of an unexposed part by setting it as the said upper limit or less. 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 more preferably 1% by mass or more in the total solid content. Is more preferable, 1.5% by mass or more is more preferable, 1.8% by mass or more is particularly preferable, 40% by mass or less is preferable, 30% by mass or less is more preferable, and 20% by mass or less is more preferable. 10 mass% or less is still more preferable, and 5 mass% or less is especially preferable. When the amount is not less than the lower limit value, there is a tendency that a decrease in sensitivity to the exposure light beam can be suppressed, and when the value is not more than the upper limit value, a decrease in solubility in a developing solution in an unexposed portion and a development defect associated therewith are suppressed. There is a tendency to be able to.

[(E ′) Thermal Polymerization Initiating Component]
Specific examples of the (E ′) thermal polymerization initiation component that may be contained in the colored resin composition of the present invention include azo compounds, organic peroxides, and hydrogen peroxide. Of these, azo compounds are preferably used. More specifically, for example, a thermal polymerization initiating component described in International Publication No. 2009/107734 can be used.
These thermal polymerization initiating 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 quencher and an antioxidant in addition to the above components. In addition, at least one of a surfactant, an organic carboxylic acid and an organic carboxylic acid anhydride, a thermosetting compound, a plasticizer, a thermal polymerization inhibitor, a storage stabilizer, a surface protective agent, an adhesion improver, a development improver, etc. You may contain. As these optional components, for example, various compounds described in JP-A-2007-113000 can be used. Moreover, when it contains a pigment, you may contain a dispersing agent and a dispersing aid.

[Quencher]
The quencher is not particularly limited as long as it has absorption near the wavelength of fluorescence emitted by the xanthene dye represented by the general formula (I). For example, metal complex dyes, anthraquinone dyes, phthalocyanine dyes , Tetraazaporphyrin dyes, triarylmethane dyes, metal complex dyes and the like are preferable.

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

  Specific examples of the metal complex dye include 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; 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. Acid red 211, metal complex dyes described in JP 2010-170117 A, JP 2013-7032 A, and the like. These may be used alone or in combination of two or more.

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

  Examples of anthraquinone dyes 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. Disperse Blue 60, those described in International Publication No. 2014/012814, Japanese Patent Application Laid-Open No. 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 etc. are mentioned.

  Examples of tetraazaporphyrin-based dyes include those described in International Publication No. 2014/012814.

  Examples of triarylmethane dyes include C.I. I. Acid Blue 86, C.I. I. Acid Blue 88, C.I. I. Acid Blue 108, International Publication No. 2009/107734, International Publication No. 2011/162217, International Publication No. 2015/080217, and the like.

  Although it does not specifically limit about the content rate of the quencher in the colored resin composition of this invention, 1 mass% or more is preferable in all the solid content in a total solid, 2 mass% or more is more preferable, and 3 mass% or more is More preferably, 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. There is a tendency that the contrast tends to be improved by setting it to the lower limit value or more, and it is possible to suppress a decrease in luminance by setting the upper limit value or less.

[Antioxidant]
Antioxidant means the compound which suppresses the fall of the brightness | luminance of dyes, such as a xanthene dye represented by the said general formula (I). Although it will not specifically limit if the fall of the brightness | luminance of dye is suppressed, The point that the capability to capture | acquire the peroxy radical which accelerates | stimulates decomposition | disassembly of a dye is high, and the compatibility with a colored resin composition is high, and acquisition is. It is preferable that it is a compound represented by the following formula (i) at the point which is easy.

In the above formula, R ^A and R ^B each independently represents 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 the bivalent group which consists of a C1-C10 alkylene group and / or ester bond which may have a substituent.

In addition to R ^A and R ^B , —OH, and Z, the benzene ring in the above formula may have an arbitrary substituent.
m represents an integer of 1 to 4.
In addition, when m is an integer of 2 or more, a plurality of molecules included in one molecule

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

(R ^A and R ^B )
R ^A and R ^B each independently represents 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.
In addition, the number of carbon atoms is preferably 1 to 20, more preferably 3 to 10 from the viewpoint that many chemical conjugated structures can be taken since 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 heterocyclic ring.
The aromatic hydrocarbon ring may be a single ring or a condensed ring, and is not particularly limited as long as the number of carbon atoms forming the ring is 5 to 10. For example, m free valences are Benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, and the like.

  The aromatic heterocyclic ring may be a single ring or a condensed 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 valences Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring , Thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline Ring, quinoxaline ring, phenanthridine ring, ben Imidazole ring, perimidine ring, a quinazoline ring, a quinazolinone ring, and azulene ring.

The free valence in the present invention is based on the description in “Organic Chemistry / Biochemical Nomenclature” (Nanedo, published May 20, 1992, translated by Kenzo Hirayama and Kazuo Hirayama, pages 11-12). It is.
On the other hand, the heterocyclic group may be a single ring or a condensed ring. Examples of the atoms 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, these may be the same or different.

Specific examples include a pyridinyl group, a quinolinyl group, an isoquinolinyl group, a benzothiazolinyl group, a phthalimidoyl group, a piperidinyl group, and a pyrrolidinyl group.
Among the aromatic ring and heterocyclic ring in L, the compound is represented by the following <Group A> in that it is excellent in compatibility with the binder resin in the colored resin composition and has a stable structure after radical scavenging. The group is particularly preferred.

  Each * in the above structure independently represents a bonding site with Z, a hydrogen atom, or an arbitrary substituent. However, in each ring, at least one of * represents a bonding 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 an alkylene having 1 to 10 carbon atoms which may have a substituent. It may be a group combined with an ester bond.
Examples of the combined group also include groups such as —CH ₂ —C (═O) O—CH ₂ —.

The number of constituent atoms of Z is preferably 30 or less. Moreover, in a C1-C10 alkylene group, it is preferable that it is C1-C5 from a viewpoint of the ease of a synthetic reaction, and it is more preferable that it is 1 or 2.
The benzene ring in the formula (i) may have an arbitrary substituent in addition to R ^A , R ^B , —OH, and Z, but the substituent is high in that it has a high bonding force with a radical. It is preferable not to have.
Examples of the substituent that the alkyl group in R ^A and R ^B , the aromatic ring group and heterocyclic group in L, the alkylene group in Z, and the benzene ring in the above formula may have the following (substitution group W2) Is mentioned.

(Substituent group W2)
Fluorine atom, chlorine atom, alkyl group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms, alkoxyl group having 1 to 8 carbon atoms, phenyl group, mesityl group, tolyl group, naphthyl group, cyano group, acetyloxy Group, alkyl carboxyl group having 2 to 9 carbon atoms, sulfonic acid amide group, sulfone alkylamide group having 2 to 9 carbon atoms, alkylcarbonyl group having 2 to 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, or an alkylthio group having 1 to 8 carbon atoms, which is formed by bonding an alkyl group having 1 to 4 carbon atoms.

(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 2-4.

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

In the above formula, R ^A, R ^B , L, and m have the same meanings as in the formula (i).
n represents an integer of 1 to 10.
l represents an integer of 0 to 5.
The benzene ring in the above formula may have an optional substituent other than R ^A and R ^B , —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.
In addition, when m is an integer of 2 or more, a plurality of molecules included in one molecule

May be the same structure or different.
* Represents a binding site to L.

(N)
n represents an integer of 1 to 10.
Preferably it is an integer of 1-5 from the point with high compatibility with binder resin etc. and favorable antioxidant performance.

(About l)
l represents an integer of 0 to 5.
From the viewpoint of high compatibility with a binder resin and the like and good antioxidation performance, it is preferably an integer of 0 to 1.

(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, more preferably 1300 or less. It is preferable in the said range at the point with high bond strength with a radical.

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

  Among these, IRGANOX1010, IRGANOX1035, IRGANOX1330 or ADEKA STAB AO-20 are preferable, IRGANOX1010, IRGANOX1035 or IRAGANOX1330 is more preferable, and IRGANOX1010 is further more preferable from the viewpoint of high antioxidant ability.

  The content of the antioxidant is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, and more preferably 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, there is little precipitation of unnecessary materials, high antioxidant ability can be exhibited, and a decrease in luminance can be suppressed.

[Dispersant]
When the colored resin composition of this invention contains a pigment, it is preferable to contain a dispersing agent further.
The dispersant in the present invention is not particularly limited as long as the pigment is dispersed and can maintain stability.
For example, cationic, anionic, nonionic or amphoteric dispersants can be used, but polymer dispersants are preferred. Specific examples include block copolymers, polyurethanes, polyesters, alkylammonium salts or phosphate esters of polymer copolymers, and cationic comb graft polymers. Of these dispersants, block copolymers, polyurethanes, and cationic comb graft polymers are preferred. In particular, a block copolymer is preferable, and among these, a block copolymer composed of an A block having solvophilicity and a B block having a functional group containing a nitrogen atom is preferable.

Specifically, the B block having a nitrogen atom-containing functional group includes a unit structure having at least one of a quaternary ammonium base and an amino group in the side chain, while the solvophilic A block is a quaternary. A unit structure having no ammonium base and amino group 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 has a pigment adsorption function.

When the B block has a quaternary ammonium base, 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.

Moreover, 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 weight, particularly 5 to 500 parts by weight, especially 10 to 250 parts with respect to 100 parts by weight of the total pigment content. It is preferable to use so that it may become in the range of a mass part.
By setting it within the above range, preferable pigment dispersibility can be secured, and the pigment dispersion stability is more preferable.

[Dispersion aid]
The colored resin composition of the present invention may contain a dispersion aid. The dispersion aid here may be a pigment derivative. Examples of the pigment derivative include JP-A Nos. 2001-220520, 2001-271004, 2002-179976, and 2007-. Various compounds described in Japanese Patent Application Publication No. 113000 and Japanese Patent Application Publication No. 2007-186681 can be used.

  The content 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. Preferably it is 10 mass% or less, More preferably, it is 5 mass% or less. By controlling the addition amount within the above range, it is preferable in that the effect as a dispersion aid is exhibited and 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. For example, (A) a colorant and (C) a binder resin containing a xanthene dye represented by the general formula (I). Can be prepared by mixing with (B) a solvent and optional components used as necessary.

Alternatively, a color material-containing liquid containing (A) a color material and (B) a solvent may be prepared, and (C) a binder resin and an optional component may be mixed therewith.
In addition, as a preparation method in the case of including a pigment, in the presence of a dispersant and, if necessary, a dispersion aid to be added in a solvent including a pigment, optionally together with a part of the binder resin (C), for example, paint Using a shaker, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like, a pigment dispersion is prepared by mixing and dispersing while grinding. Xanthene dye (I), (C) binder resin, and (D) polymerizable monomer, (E) at least one of photopolymerization initiation component and thermal polymerization initiation component, etc. The method of preparing by adding and mixing can be mentioned.
On the other hand, when a pigment is not included, for example, as a preparation method when only a dye is used as a coloring material, a dispersing agent or a dispersion aid is not required, and a complicated pigment dispersion step is not required. The composition can be produced at a low cost.

[Application of colored resin composition]
The colored resin composition of the present invention is usually in a state where all the constituent components are dissolved or dispersed in a solvent. Such a colored resin composition is supplied onto a substrate to form components such as a color filter, a liquid crystal display device, and an organic EL display device.
Hereinafter, as an application example of the colored resin composition of the present invention, an application as a pixel of a color filter and an image display apparatus 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 using the colored resin composition of the present invention.
The method for forming the color filter of the present invention will be described below.
The pixel of the color filter can be formed by various methods. Here, although the case where it forms by the photolithographic method using a photopolymerizable colored resin composition is demonstrated to an example, a manufacturing method is not limited to this.

  First, on the surface of the substrate, if necessary, a black matrix is formed so as to partition a portion for forming pixels, and after applying the colored resin composition of the present invention on this substrate, pre-baking is performed. The solvent is evaporated to form a coating film. Then, after exposing this coating film through a photomask, developing with an alkali developer, dissolving and removing the unexposed portion of the coating film, and then post-baking, each of red, green, and blue A color filter can be manufactured by forming a pixel pattern.

In the present invention, it is particularly preferable that the pixel formed using the colored resin composition of the present invention is a red pixel.
The substrate used for forming the pixels is not particularly limited as long as it is transparent and has an appropriate strength. For example, polyester resin, polyolefin resin, polycarbonate resin, acrylic resin, thermoplastic resin Examples thereof include a sheet made, an epoxy resin, a thermosetting resin, and various glasses.

In addition, these substrates may be appropriately subjected to pretreatment as desired, such as thin film formation treatment with a silane coupling agent or urethane resin, surface treatment such as corona discharge treatment or ozone treatment, if desired.
When applying the colored resin composition to the substrate, a spinner method, a wire bar method, a flow coating method, a slit and spin method, a die coating method, a roll coating method, a spray coating method, and the like can be given. Of these, the slit and spin method and the die coating method are preferable.

The thickness of the coating film is usually 0.2 to 20 μm, preferably 0.5 to 10 μm, 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 can be easily adjusted in the pattern development or liquid crystal cell forming step, and a desired color can be easily expressed.
As the radiation used in the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.

  A light source for using radiation having a wavelength of 190 to 450 nm used for image exposure is not particularly limited. 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, Lamp light sources such as medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp; laser light sources such as argon ion laser, YAG laser, excimer laser, nitrogen laser, helium cadmium laser, semiconductor laser, and the like. An optical filter can also be used when used by irradiating light of a specific wavelength.

Exposure of radiation, 10~10,000J / m ² is preferred.
Examples of the alkaline developer include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, 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-isopropanol Amines, tri - isopropanolamine, ethyleneimine, ethylene diimine, tetramethyl ammonium hydroxide (TMAH), an aqueous solution of an organic alkaline compound such as choline and the like are 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 the like can be added to the alkali developer. In addition, it is usually washed with water after alkali development.
As the development processing method, any method such as an immersion development method, a spray development method, a brush development method, and an ultrasonic development method can be used. The development conditions are preferably 5 to 300 seconds at room temperature (23 ° C.).

  There are no particular restrictions on the conditions of the development processing, but the development temperature is usually 10 ° C. or higher, especially 15 ° C. or higher, more preferably 20 ° C. or higher, and usually 50 ° C. or lower, especially 45 ° C. or lower, more preferably 40 ° C. or lower. Is preferred. The developing method can be any one of immersion developing method, spray developing method, brush developing method, ultrasonic developing method and the like.

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

<Image display device>
The image display device of the present invention has the above-described 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-described color filter of the present invention. There is no restriction | limiting in particular about the model and structure of the liquid crystal display device of this invention, It can assemble in accordance with a conventional method using the color filter of this invention.
For example, the liquid crystal display device of the present invention can be formed by the method described in “Liquid Crystal Device Handbook” (Nikkan Kogyo Shimbun, September 29, 1989, Japan Society for the Promotion of Science 142nd Committee).

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

  As a method for laminating the organic light emitter 500, a transparent anode 50, a hole injection layer 51, a hole transport layer 52, a light emitting layer 53, an electron injection layer 54, and a cathode 55 are sequentially formed on the upper surface of the color filter. For example, a method of adhering the organic light-emitting body 500 formed on another substrate onto the inorganic oxide film 40 can be used. The organic EL element 100 manufactured as described above can be applied to both a passive drive type organic EL display device and an active drive type organic EL display device.

Next, although a synthesis example, an Example, and a comparative example are given and this invention is demonstrated more concretely, this invention is not limited to a following example, unless the summary is exceeded.
<Synthesis of dye>
(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 added. Stir for 17 hours under reflux. The reaction solution 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 converted into N, N-dimethylformamide (40 mL). After dissolution, potassium carbonate (2.1 g, 15.0 mmol) and tetranormal butyl ammonium bromide (194 mg, 0.60 mmol) were added, and the mixture was stirred at 80 ° C. for 6 hours. Cool to room temperature and add the reaction 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)), and dye A (6.5 g, yield 90) as a red amorphous solid. %).
Dye A was dissolved in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio) by 10 mass ppm. At this time, the maximum absorption wavelength (λmax) was 546 nm, and the Gram extinction coefficient (g) was 122.9 g ⁻¹ cm ⁻¹ . The result of liquid chromatography mass spectrometry of this dye A is 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}

  Under a nitrogen atmosphere, 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), and triethylamine (36.0 mL) was cooled with ice. 260 mmol) was added dropwise, and the mixture was stirred at room temperature for 10 hours. The reaction solution was washed twice with water (200 mL), and the organic layer was concentrated to obtain a transparent oily compound 3 (37.5 g, yield: quantitative).

  {Synthesis of Dye B}

In the same manner as for dye A, from compound 2 (10.3 g, 18.0 mmol) and compound 3 (18.0 g, 64.9 mmol), dye B (16.5 g, 94% yield) was obtained as a red amorphous solid. Was synthesized.
Dye B was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). The maximum absorption wavelength (λmax) at this time was 544 nm, and the Gram extinction coefficient (g) was 125.2 g ⁻¹ cm ⁻¹ . The result of liquid chromatography mass spectrometry of this dye B is 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 .81 g, 27.9 mmol) was added little by little, and the mixture was stirred 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 give oily compound 4 (4.43 g).

  {Synthesis of Dye C}

Under nitrogen atmosphere, 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) 0.13 mmol), N, N-dimethylformamide (10 mL) was added, and the mixture was heated to 80 ° C. and stirred for 17 hours. After completion of the reaction, the reaction solution was poured into water (20 mL) and extracted with chloroform (50 mL), and then the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The desiccant was filtered off, the solvent was distilled off, and the solid obtained 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)) to obtain red solid dye C (1.13 g, yield 42%).
Dye C was dissolved by 10 mass ppm in propylene glycol monomethyl acetate (PGMEA) / propylene glycol monomethyl ether (PGME) = 35/65 (volume ratio). At this time, the maximum absorption wavelength (λmax) was 544 nm, and the Gram extinction coefficient (g) was 112 Lg ⁻¹ cm ⁻¹ . The result of liquid chromatography mass spectrometry of this dye C is 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}

  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 under a nitrogen atmosphere. (2.81 g, 27.9 mmol) was added little by little, and the mixture was stirred 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 give oily compound 5 (4.1 g).

  {Synthesis of Dye D}

Under a 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 mmol) .26 mmol) was added N, N-dimethylformamide (10 mL), heated to 80 ° C., and stirred for 17.5 hours. After completion of the reaction, the reaction solution was poured into water (20 mL) and extracted with chloroform (50 mL), and then the organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The desiccant was removed by filtration, the solid obtained by distilling off the solvent 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)) 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 mass ppm. At this time, the maximum absorption wavelength (λmax) was 544 nm, and the Gram extinction coefficient (g) was 110 Lg ⁻¹ cm ⁻¹ . The result of liquid chromatograph-mass spectrometry of this dye D is 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 being replaced 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 mixture of 8.47 parts by mass of nitrile was added dropwise over 3 hours, and the mixture was further stirred at 90 ° C. for 2 hours. Next, the inside of the reaction vessel was changed to air substitution, 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. Thereafter, 15.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.2 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight Mw in terms of polystyrene 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 was 40% by mass and used as Resin A.

(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, acrylic acid 102 parts by mass, p-methoxyphenol 0.3 part by mass, triphenylphosphine 5 parts by mass, and propylene glycol monomethyl The reaction vessel was charged with 264 parts by mass of ether acetate (PGMEA) and stirred at 95 ° C. until the acid value was 3 mg-KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.2 mgKOH / g). Subsequently, 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 mg KOH / g and a polystyrene-reduced 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 used as Resin B.

(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 Chemical Co., Ltd.) having a tricyclodecane skeleton, 43.2 parts by mass of acrylic acid, tetrahydrophthalic anhydride (THPA) Synthesis was performed in the same manner as in Synthesis Example 5 except that 59.3 parts by mass were used. The weight average molecular weight Mw in terms of polystyrene 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 the resin solution so that the solid content was 40% by mass, and used as Resin C.

(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 Chemical Co., Ltd.) having a tricyclodecane skeleton, 43.2 parts by mass of acrylic acid, tetrahydrophthalic anhydride (THPA) Synthesis was performed in the same manner as in Synthesis Example 5 except that 19.8 parts by mass were used. The weight average molecular weight Mw in terms of polystyrene 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 the resin solution so that the solid content was 40% by mass and used as Resin D.

(Synthesis Example 9: Synthesis of initiator A)
As initiator A, 3- (2-acetoxyimino-1,5-dioxo-5-methoxypentyl) -9-ethyl-6- (o-toluoyl) -9H- was prepared by the method described in WO2009 / 131189. Carbazole was synthesized.

[Preparation of colored resin compositions 1 to 4]
The dyes A to D obtained in the synthesis examples 1 to 4 and the resins A and B obtained in the synthesis examples 5 and 6 are mixed with other components so as to have the composition described in the following Table 1, and colored. Resin compositions 1 to 4 were prepared. In mixing, the components were stirred for 1 hour or more until they were sufficiently mixed, and finally filtered through a 5 μm piece filter to remove foreign matters.
In addition, the numerical value of the upper stage in Table 1 represents the content rate (mass%) in the colored resin composition of each component to add, and the numerical value of the lower stage is the content ratio (mass%) in the total solid content of each component. ).

In addition, each compound of Table 1 is as follows, respectively.
RS72K: Mega-Fac RS-72-K, perfluoroalkyl group-containing polymer, DIC Corporation Irganox 1010: Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propinate], BASF JPP -100: Tetraphenyldipropylene glycol diphosphite, manufactured by Johoku Chemical Industry Co., Ltd. PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[Evaluation of heat resistance]
On the glass substrate cut into 5 cm square, the chromaticity y value after post baking is 0.175 for each colored resin composition prepared in [Preparation of colored resin compositions 1 to 4] by spin coating. After being applied and dried under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 60 mJ / cm ^{2 and} then 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 chromaticity x, y (C light source) and luminance LY in the XYZ color system and the color difference before and after post-baking. ΔE ^* ab was calculated. The results are shown in Table 2.

[Evaluation of light resistance]
On a glass substrate cut into 5 cm square, the chromaticity y value after post baking is 0.175 for each colored resin composition prepared in [Preparation of colored resin compositions 1 to 4] by spin coating. After being applied and dried under reduced pressure, it was pre-baked on a hot plate at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed with 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 chromaticity x, y (C light source) was calculated. Next, a weatherometer Ci4000 (manufactured by Atlas Co., Ltd.) was set through the polarizing plate having the transmittance shown in FIG. 2, and simulated sunlight was irradiated for 20 hours. Thereafter, the spectral transmittance of the film after irradiation was measured in the same manner, and 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]
About the synthesized dyes A to D, solubility in propylene glycol monomethyl ether acetate (manufactured by Daicel Chemical Industries) was evaluated by the following procedure.
First, 50 mg of dye and 450 mg of propylene glycol monomethyl ether acetate were mixed in a 5 mL glass container, stirred for 1 hour, and 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.
○ (Solubility): No residue at the bottom of the container × (Insoluble): Residue at the bottom of the container

[Preparation of colored resin composition for red pixel]
(Synthesis Example 10: Synthesis of Red Pigment 1)
An alcoholate was synthesized by reacting 200 parts by mass of t-amyl alcohol and 140 parts by mass of sodium-t-amyl alkoxide at 100 ° C. in a nitrogen atmosphere. This was heated to 60 ° C., a mixed liquid 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 liquid temperature became 85 ° C. or lower. This suspension was further stirred for 15 hours or more, and then added to a mixed solution 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 solid content was washed with methanol and water repeatedly until there was no coloration. It dried until it became constant weight with a 80 degreeC vacuum dryer, and the red pigment 1 (150 mass parts) was obtained.

(Synthesis Example 11: Synthesis of Resin E)
Prepare a separable flask with a cooling tube as a reaction vessel, charge 400 parts by mass of propylene glycol monomethyl ether acetate, purge with nitrogen, and heat in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. did.
Meanwhile, 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, t-butylperoxy-2-ethyl in the monomer tank Charge 5.2 parts by weight of hexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate, and 5.2 parts by weight of n-dodecyl mercaptan and 27 parts by weight of propylene glycol monomethyl ether acetate in a chain transfer agent tank After stabilizing at 90 ° C., dropping was started from the monomer tank and the chain transfer agent tank to initiate polymerization. While maintaining the temperature at 90 ° C., dropping was carried out over 135 minutes each, and 60 minutes after the dropping was finished, the temperature was raised and the reaction vessel was brought to 110 ° C. After maintaining at 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 39.6 parts of glycidyl methacrylate, 0.4 part of 2,2′-methylenebis (4-methyl-6-tert-butylphenol) and 0.8 part of triethylamine were charged into the reaction vessel and left at 110 ° C. for 9 hours. 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 pigment dispersion 1)
9.47 parts by mass of red pigment 1, 2.37 parts by mass of BYK-LPN6919 (produced by Big Chemie) as a dispersant, 3.15 parts by mass of resin E in terms of solids, propylene glycol monomethyl ether acetate 60.00 parts by mass (including those derived from the dispersant and resin E) and 225 parts by mass of zirconia beads having a diameter of 0.5 mm are filled in a stainless steel container and dispersed in a paint shaker for 6 hours to prepare Dye Dispersion 1 did.

(Preparation of colored resin composition 5)
Dye dispersion 1 containing red pigment 1, Dye B obtained in Synthesis Example 2 and Resins C and D obtained in Synthesis Examples 7 and 8 were added to other components so as to have the composition described in Table 5 below. And a colored resin composition 5 was prepared. In the preparation, first, the dye B, the quencher A and the solvent are thoroughly stirred and dissolved, and then the pigment dispersion 1 is added thereto, stirred for 20 minutes, and then a red liquid which is ultrasonically dispersed for 10 minutes is first obtained. Then, other components were added thereto and stirred for 1 hour or more until they were sufficiently mixed. Finally, the mixture was filtered through a 5 μm piece filter to remove foreign matters.
In addition, the numerical value of the upper stage in Table 5 represents the content rate (mass%) in each colored resin composition of each component to add, and the numerical value of a lower stage is the content ratio (mass%) in the total solid of each component. ).

In addition, each compound of Table 5 is as follows, respectively.
BYK330: BYK-330, silicon surfactant (manufactured by DIC)
Quencher A: Variast Orange 3209 (Orient Chemical Co., Ltd.)

[Evaluation of heat resistance]
The colored resin composition 5 is applied onto a glass substrate cut into 5 cm square by spin coating so that the chromaticity y value after post-baking is 0.326, dried under reduced pressure, and then on a hot plate. And prebaked at 80 ° C. for 3 minutes. Thereafter, the entire surface was exposed at an exposure amount of 40 mJ / cm ^{2 and} then post-baked 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. ΔE ^* ab was calculated. The results are shown in Table 6.

[Evaluation of contrast]
The film after the post-baking of the colored resin composition 5 obtained in the above [Evaluation of heat resistance] is subjected to a contrast measuring device (contrast tester CT-1 (manufactured by Aisaka Electric Co., Ltd.), It was installed in BM-5AS (Topcon Corporation, luminance meter), F-10 light source (polarizing plate insertion)), and the contrast was measured with a blank value of 18000. The results are shown in Table 6.

[Evaluation of light resistance]
The film after post-baking of the colored resin composition 5 obtained in [Evaluation of heat resistance] is set on a weatherometer Ci4000 (manufactured by Atlas Co., Ltd.) through a polarizing plate having the transmittance shown in FIG. The artificial sunlight was irradiated for 40 hours. Thereafter, the spectral transmittance of the film after irradiation was measured in the same manner as in [Evaluation of heat resistance], and 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 apparent from Tables 2, 4 and 6, the colored resin compositions of Examples 1 to 5 contain a dye that is sufficiently dissolved in a solvent and is excellent in luminance.

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. As a result, twisting and rotational movement of the side chain is facilitated, and at least one of the methylene groups constituting the alkylene group in X ¹ and X ² is replaced with a polar group, so that the affinity with the solvent is increased. It is considered that the solubility is higher and the solubility is higher.

  In particular, the colored resin composition for red pixels of Example 5 exhibits very high luminance in red pixel applications. The transmission spectrum of xanthene dyes 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, and therefore red when combined with these pigments. It is considered that a red pixel with higher luminance can be obtained by creating the pixel. Further, in order to improve luminance, a spectral shape that transmits a wavelength around 560 to 650 nm as much as possible and absorbs a wavelength less than 560 nm as much as possible is preferable, and a rectangular spectrum is ideal. If the solubility of the coloring material is high, the absorbance increases due to dissolution at the molecular level, and thus it is considered that the luminance is higher as it approaches a rectangular spectrum.

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 is not clarified, by including the xanthene dye represented by the general formula (I), the π-π interaction and hydrophobicity of the benzene ring bonded to X ¹ and X ² It is considered that the light resistance is enhanced because the interaction easily causes stacking between molecules and easily causes deactivation of the excited state.

DESCRIPTION OF SYMBOLS 100 Organic EL element 10 Transparent support substrate 20 Pixel 30 Organic protective layer 40 Inorganic oxide film 50 Transparent anode

Claims (7)

(A) a coloring resin composition containing a coloring material, (B) a solvent, and (C) a binder resin,
The colored resin composition, wherein the color 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 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a halogen atom.
h to k each independently represents an integer of 0 to 5, and l and m each independently represents an integer of 0 to 3.
X ¹ and X ² each independently represents an alkylene group which may have a substituent, and one or more of methylene groups constituting the alkylene group are —O—, —S—, —CO—, and — NR ⁷ - and substituted with at least one selected from the group consisting of. 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 (A) coloring material further contains a red pigment.   The colored resin composition according to claim 1 or 2, further comprising (D) a polymerizable monomer.   The colored resin composition according to claim 1, further comprising (E) a photopolymerization initiation component and / or (E ′) a thermal polymerization initiation component.   Furthermore, the coloring resin composition of any one of Claims 1-4 containing antioxidant.   The color filter which has a pixel formed using the colored resin composition of any one of Claims 1-5.   An image display device comprising the color filter according to claim 6.

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