JP6969489B2 - Red coloring composition for organic EL display device, color filter, and organic EL display device - Google Patents

Description

INDUSTRIAL APPLICABILITY The present invention relates to a red coloring composition for an organic EL display device, a color filter, which is preferably used for a color display device using a white light emitting organic EL (electroluminescence) element (hereinafter, may be referred to as "organic EL element"). And color display devices. Note that white means a broad concept including pseudo-white.

As a color display device using a color filter, for example, (i) a combination of a backlight as a light source, a liquid crystal as a light shutter, and a color filter having a color adjustment function (color conversion function, color separation function, color correction function, etc.). Examples thereof include a liquid crystal display device including, (ii) a synthetic white organic EL light source, and an organic EL display device composed of a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.).

Currently, the liquid crystal display of (i) is the mainstream of flat panel displays, and because of its advantages such as low power consumption and space saving, various types such as personal computer monitors, mobile phone displays, notebook personal computers, and mobile information terminals are available. In recent years, it has also been used for LCD TVs in place of conventional brown tube TVs. Color reproducibility is important in LCD TV applications. The color reproducibility of the color liquid crystal display device is determined by the color of the light emitted from the red, green, and blue filter segments, and the chromaticity points of the respective filter segments are set to (xR, yR), (xG, yG), respectively. When (xB, yB), it is evaluated by the area of the triangle surrounded by these three points on the xy chromaticity diagram, and the three primary colors of the standard method defined by the American National Television System Committee (NTSC), red. As a ratio to the area surrounded by (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08) (unit is%, hereinafter abbreviated as NTSC ratio). Be expressed. This value is 40 to 100% for a general notebook computer, 50 to 100% for a monitor for a personal computer, and 70% to 100% for a liquid crystal television.

As the backlight in the liquid crystal display device (i), a cold cathode tube type backlight, a pseudo-white backlight having a two-wavelength peak and a backlight having a three-wavelength peak using a light emitting diode using an inorganic material and an organic EL element are used. and so on. In the liquid crystal display device, the liquid crystal layer sandwiched between the two polarizing plates controls the degree of polarization of the light passing through the first polarizing plate to control the amount of light passing through the second polarizing plate. There are VA mode, IPS mode, and the like, and among them, the type using a TN (twisted nematic) mode type liquid crystal display is the mainstream. However, these liquid crystal display devices have a problem that energy is wasted because the backlight unit continues to emit the same light as the white display even in the black display.

As the synthetic white light source of the organic EL display device of (ii), there are a light source having a two-wavelength peak, a light source having a three-wavelength peak, and a light source having a large number of peaks in the visible light region, and an organic EL material that emits light in each color is used. Synthetic white light is obtained by mixing or layering.

Since the organic EL display device can directly control the light source of the pixel on / off by using a TFT (thin film transistor) or the like, it is possible to display black by extinguishing the light emission of the designated pixel. Therefore, the polarizing plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control by the liquid crystal body. Therefore, the amount of transmitted light in the display device is increased, and the energy consumption can be significantly reduced by turning off the light emitting device in the black display. In addition, it is possible to reproduce true dark black, and the contrast ratio can be increased. As an organic EL color display device that solves the problems in such a liquid crystal display device, for example, a product such as "XEL-1" manufactured by Sony Corporation has already been put on the market. (See, for example, Patent Document 1)

However, the light emitting device using such an organic EL element has a different light emitting spectrum from the light emitting spectrum of the light source conventionally used. For example, a conventional light source has a peak in the vicinity of 420 to 430 nm, but a light source using an organic EL element has no peak in the vicinity of 420 to 430 nm due to the characteristics of the material and has a peak in the vicinity of 460 nm. Further, since the emission spectrum of the light source using the organic EL element has a broad peak as a whole as compared with the conventional light source, even after passing the peak near 460 nm, the conventional light source reaches around 500 nm. The spectrum is higher. For these reasons, the current situation is that the color filter currently used cannot be used as it is in a display device using a light source using an organic EL element. Therefore, it is necessary to select and develop a color filter material having optimum hue and transmittance characteristics that can be used as a light source using an organic EL element.

Even in an organic EL display device having such a light source, it is required to increase the NTSC ratio as in the liquid crystal display device. In order to increase the NTSC ratio, it is necessary to increase the color purity of each filter segment, but if the color purity is increased, the light utilization efficiency of the light source (expressed by the brightness Y value) decreases, so the power consumption There is a problem that the number increases.

Conventionally, in order to obtain a color filter having a large NTSC ratio, C.I. I. Pigment Red 177, C.I. I. Pigment Red 179 and other red pigments and C.I. I. Pigment Yellow 185 and C.I. I. Pigment Yellow 139 and other yellow pigments are often used.

Here, when the above pigments are used alone or in combination, there is a problem that the brightness is low.

In Patent Documents 2 to 4, in order to further improve the brightness of the red filter segment, C.I. I. Pigment Red 176, C.I. I. Pigment Red 242, and C.I. I. It has been proposed to use an azo pigment such as Pigment Orange 38 as a main pigment, but the brightness and color purity are not sufficient, and further improvement is required.

Japanese Unexamined Patent Publication No. 2005-100921 Japanese Unexamined Patent Publication No. 2009-237462 Japanese Unexamined Patent Publication No. 11-14824 Japanese Unexamined Patent Publication No. 10-115709

The coloring composition of the present invention can provide a color filter that can satisfy the two characteristics of high brightness and high purity in an organic EL display device using a white light emitting organic EL element as a light source. Another object of the present invention is to provide a color display device that can achieve the quality required as a color filter for an organic EL display device such as a high NTSC ratio.

As a result of diligent studies, the present inventors have found that the above-mentioned problems can be solved by a red coloring composition containing an azo pigment having a specific structure, and have reached the present invention.

［一般式（１）中、Ｒ₁は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表す。Ｒ₂およびＲ₃は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基を表す。
Ｘ₁〜Ｘ₄は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、ヒドロキシル基、シアノ基、ニトロ基、カルボキシル基、スルホ基、ハロゲン原子を表す。］

一般式（２）

［一般式（２）中、Ｒ₄は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表す。Ｒ₅およびＲ₆は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基を表す。
Ｘ₅〜Ｘ₁₂は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、ヒドロキシル基、シアノ基、ニトロ基、ハロゲン原子を表す。Ａは、直接結合、または２価の連結基を表す。２価の連結基としては、置換基を有してもよいアルキレン基、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ₂−、−ＣＯＯ−、−ＣＯＮＨ−、−ＳＯ₂ＮＨ−を表す。］ That is, the present invention relates to a colorant containing the azo pigment [A] represented by the following general formula (1) and or (2), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator [B]. The present invention relates to a red coloring composition for an organic EL display device containing the above.

General formula (1)

[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. .. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
Independently, X _{1 to} X ₄ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group and a sulfo group. , Represents a halogen atom. ]

General formula (2)

[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. .. R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X _{5 to} X ₁₂ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, and a halogen atom. A represents a direct bond or a divalent linking group. As the divalent linking group, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO _2- , -COO-, -CONH-, and -SO ₂ NH- are used. show. ]

［一般式（３）中、Ｚ₁〜Ｚ₁₃は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリール基、−ＳＯ₃Ｈ、−ＣＯＯＨ、およびこれら酸性基の１価〜３価の金属塩、アルキルアンモニウム塩、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を示す。
Ｚ₁〜Ｚ₄、および／または、Ｚ₁₀〜Ｚ₁₃の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する場合がある。］ Further, in the present invention, the colorant is further described as C.I. I. The present invention relates to the red coloring composition for an organic EL display device, which comprises Pigment Yellow 139 and at least one pigment selected from the quinophthalone compound represented by the following general formula (3).

General formula (3)

[In the general formula (3), Z _{1 to} Z ₁₃ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The sulfamoyl group which may have is shown.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may together form an aromatic ring that may have a substituent. ]

The present invention also relates to the red coloring composition for an organic EL display device, wherein the photopolymerization initiator [B] contains an oxime ester compound [B1].

Further, in the present invention, in a color filter for an organic EL display device including at least one red filter segment, at least one green filter segment and at least one blue filter segment, at least one red filter segment is the organic EL described above. The present invention relates to a color filter for an organic EL display device formed by a red coloring composition for a display device.

_{Further, the present invention has peak wavelengths λ 1} and λ ₂ that maximize the emission intensity in at least the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, respectively, and the emission intensity I ₁ and the wavelength λ at the wavelength λ 1 respectively. _{When a} white organic EL light source having spectral characteristics in which the ratio of emission intensity I _{2 (I 2} / I ₁ ) in 2 is 0.4 or more and 0.9 or less is used, the color of the colored film in the XYZ color system is used. When the degree coordinates are (xR, yR), (xG, yG), and (xB, yB), respectively, the areas of the triangle surrounded by these three points are red (0.67, 0.33) and green (0.67, 0.33). 0.21, 0.71), formed by the red coloring composition for an organic EL display device described above, which is 75% or more of the area surrounded by blue (0.14, 0.08). The present invention relates to the color filter for an organic EL display device.

The present invention also relates to an organic EL display device including the color filter for the organic EL display device and a white organic EL light source.

_{Further, in the present invention, the white organic EL light source has peak wavelengths λ 1} and λ ₂ at which the emission intensity is maximized at least in the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, respectively, at the wavelength λ ₁ . The present invention relates to the organic EL display device, which has an emission spectrum in which the ratio (I ₂ / I ₁ ) of the emission intensity I _{2 to} the emission intensity I ₁ at the wavelength λ _{2 is 0.4 or more and 0.9 or less.}

The red coloring composition for an organic EL display device of the present invention can provide a color filter that can satisfy the two characteristics of high brightness and high purity.

This is an example of the emission spectrum of a white organic EL light source (EL-1). The horizontal axis shows the wavelength and the vertical axis shows the emission intensity.

Hereinafter, the present invention will be described in detail.
In the present application, the term "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" is particularly described. Unless there is an acryloyl and / or methacrylic acid, acrylic and / or methacrylic acid, acrylic acid and / or methacrylic acid, acrylate and / or methacrylate, or acrylamide and / or methacrylic acid, respectively. It shall be represented.
Further, "CI" mentioned in the present specification means a color index (CI).

<Red coloring composition>
First, the red coloring composition for an organic EL display device of the present invention will be described.
The red coloring composition of the present invention contains the azo pigment represented by the general formula (1) and or (2), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator. In particular, it is a red coloring composition preferably used for a color filter of a color display device provided with a white organic EL light source. First, other components such as a colorant used in the red coloring composition, a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an organic solvent used as necessary, and a dispersion aid will be sequentially described.

一般式（１）中、Ｒ₁は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表す。Ｒ₂およびＲ₃は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基を表す。
Ｘ₁〜Ｘ₄は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、ヒドロキシル基、シアノ基、ニトロ基、カルボキシル基、スルホ基、ハロゲン原子を表す。 <Colorant>
(Azo pigment [A])
The colorant of the present invention is characterized by containing the azo pigment [A] represented by the general formula (1) and / or (2).

General formula (1)

In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
Independently, X _{1 to} X ₄ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group and a sulfo group. , Represents a halogen atom.

Examples of the "halogen atom" in R ₁ include fluorine, bromine, chlorine and iodine, and among these, chlorine is preferable.

In R ₁ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, and the like. 2-Ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, dimethylcyclohexyl group and the like. Of these, a methyl group and a trifluoromethyl group are preferable.

In R ₁ , the "alkoxyl group which may have a substituent" includes a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group and a 2-ethylhexyloxy group. Examples thereof include a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, a 2- (diethylamino) ethoxy group and the like, of which a methoxy group and a trifluoromethoxy group are preferable, and a methoxy group is particularly preferable.

In R ₁ , the "aryloxy group which may have a substituent" includes a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, and a 4-chloro-2-methylphenyloxy group. Groups, 4-tert-butylphenyloxy group, 4-methoxyphenyloxy group, 4-diethylaminophenyloxy group, 4-nitrophenyloxy group and the like can be mentioned, and among these, a phenoxy group is preferable.

In R ₂ and R ₃ , the "alkyl group which may have a substituent" includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group and a tert. -Amil group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-hydroxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, Examples thereof include a cyclohexyl group and a dimethylcyclohexyl group, and a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group and a 2-hydroxyethyl group are preferable.

In R ₂ and R ₃ , the substituent of the "phenyl group which may have a substituent" may have a _{halogen atom in R 1,} an alkyl group which may have a substituent, and a substituent. Examples thereof include an alkoxyl group and an aryloxy group which may have a substituent, and in addition to these, a hydroxyl group, an amino group, -NR ₇ R ₈ , a sulfo group, -SO ₂ NR ₉ R ₁₀ , -COOR ₁₁ , -CONR ₁₂ R ₁₃ , nitro group, cyano group and the like.

R _{7 to} R ₁₃ independently represent a hydrogen atom and an alkyl group which may have a substituent, and examples of the "alkyl group which may have a substituent" include an amino group and a monoalkylamino group. Alternatively, an alkyl group substituted with a dialkylamino group is preferable.

In X _{1 to} X ₄ , the "alkyl group which may have a substituent" has the same _{meaning as that in R 1} , and a methyl group, an ethyl group and a trifluoromethyl group are preferable.

一般式（２）中、Ｒ₄は、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリールオキシ基を表す。Ｒ₅およびＲ₆は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいフェニル基を表す。
Ｘ₅〜Ｘ₁₂は、それぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、ヒドロキシル基、シアノ基、ニトロ基、ハロゲン原子を表す。Ａは、直接結合、または２価の連結基を表す。２価の連結基としては、置換基を有してもよいアルキレン基、−Ｏ−、−Ｓ−、−ＣＯ−、−ＳＯ₂−、−ＣＯＯ−、−ＣＯＮＨ−、−ＳＯ₂ＮＨ−を表す。 In X _{1 to} X ₄ , the "alkoxy group which may have a substituent" has the same meaning as that in R ₁ .

General formula (2)

In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X _{5 to} X ₁₂ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, and a halogen atom. A represents a direct bond or a divalent linking group. As the divalent linking group, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO _2- , -COO-, -CONH-, and -SO ₂ NH- are used. show.

In R ₄ , as "halogen atom", "alkyl group which may have a substituent", "alkoxyl group which may have a substituent", and "aryloxy group which may have a substituent". Is synonymous with that in _{R 1.}

In R ₅ and R ₆ , the "alkyl group which may have a substituent" and the "phenyl group which may have a substituent" are synonymous with those in _{R 2} and R _3.

In X _{5 to} X ₁₂ , the "alkyl group which may have a substituent" and the "alkoxyl group which may have a substituent" are synonymous with those _{in R 1.}

In A, examples of the alkylene group which may have a substituent include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group and an n-dodecylene. A group is mentioned, and examples of the substituent include an "alkyl group which may have a substituent" represented by _{R 1.}

The A in the general formula (2), substituents alkylene group which may have a, -O -, - S -, - CO -, - SO ₂ - is preferably, -SO ₂ among them - is Especially preferable.

(Other colorants)
In the red coloring composition for an organic EL display device of the present invention, other coloring agents such as pigments or dyes other than the above-mentioned azo pigment [A] are used in order to adjust the chromaticity, etc., as long as the effects of the present invention are not impaired. It may be used together. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

Examples of the colorant to be used in combination include azo pigments other than the azo pigment [A] such as diketopyrrolopyrrole pigment, azo, disazo, or polyazo, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, and ant. Anthraquinone pigments such as antron, indantron, pyranthron, or biolantron, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, slen pigments or Examples thereof include metal complex pigments.
Examples of the dye include xanthene dyes, azo dyes (pyridone dyes, barbituric acid dyes, metal complex dyes, etc.), disazo dyes, anthraquinone dyes, methine dyes and the like. In addition, rake pigments made from these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, and sulfonic acid amides of acidic dyes. It may be in the form of a compound or the like.

As the azo pigment other than the azo pigment [A], for example, the naphthol azo pigment represented by the general formulas (4) and (5) is preferable because of its high brightness.

［一般式（４）中、Ａは、水素原子、ベンズイミダゾロン基、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ¹は、水素原子、ハロゲン原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁷または−ＣＯＯＲ⁸を表す。Ｒ²〜Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁹、−ＣＯＯＲ¹⁰、−ＣＯＮＨＲ¹¹、−ＮＨＣＯＲ¹²または−ＳＯ₂ＮＨＲ¹³を表す。Ｒ⁷〜Ｒ¹³は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。]

[In the general formula (4), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ^{2 to} R ⁶ are independently hydrogen atom, halogen atom, cyano group, nitro group, trifluoromethyl group, alkyl group having 1 to 4 carbon atoms, −OR ⁹ , −COOR ¹⁰ , −CONHR ¹¹ , Represents -NHCOR ¹² or -SO ₂ NHR ¹³ . R ^{7 to} R ¹³ independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Among the naphthol azo pigments [C] represented by the general formula (4), preferably, the azo pigment [C1] in which at least one of ^{R 2 to} R ^{6 is a trifluoromethyl group, or R 2 to} R ⁶ An azo pigment [C2] in which at least one of them is −NHCOR ¹² is preferable because it is easy to make the pigment particles finer and the contrast ratio is excellent.

The naphthol azo pigment [C] represented by the general formula (4) is represented by C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238.245.247, 266, 268, 269, C.I. I. Violet 25, 50 and the like can be mentioned. Among these, from the viewpoint of hue and lightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, 269 are preferred.

In the general formula (4), in A, the "substituted group" of the phenyl group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, and cyano. Monovalent of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group. Examples thereof include trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group that may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, and an o-tri. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 Examples thereof include −methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group and the like. However, it is not limited to these.

Further, in A, the "substituted group" of the heterocyclic group which may have a substituent includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group and a trifluoro. A monovalent to trivalent metal of an acidic group selected from a methyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group. Examples include salts (eg, sodium salt, potassium salt, aluminum salt, etc.). Further, the "heterocycle" means an atom containing one or more heteroatoms other than carbon atoms among the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a monocyclic ring or a fused ring. Therefore, the heterocycle includes a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, an oxazole ring, a thiazole ring, an isooxazole ring, and an isothiazole ring. , Triazole ring, thiazylazole ring, oxazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent free group derived by removing a hydrogen atom from these heterocycles, and therefore, as a specific example of a heterocyclic group which may have a substituent, 2-. Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indrill group, 2-indrill group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, Examples thereof include an N-carbazolyl group.

Examples of the halogen atom in R ^{2 to} R ⁶ include fluorine, chlorine, bromine and iodine.

The alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹³ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group and an isobutyl group. , The sec-butyl group and the tert-butyl group.

As the pigment, from the viewpoint of lightness, A is preferably a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, it is preferred that R ¹ is an alkyl group or -OR ⁷ 1 to 4 carbon atoms, more preferably R ¹ is a methyl group or a methoxy group.

The colorant used in the present invention may have a chemical structure of the general formula (4) or a homovariant thereof, or may be a pigment having any crystal morphology, and may be any so-called polymorph. It may be a mixed crystal of pigments having a crystal morphology. The crystal morphology of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

［一般式（５）中、Ａ¹は、それぞれ独立して、水素原子、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ⁵¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁵⁷または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵⁷、Ｒ⁵⁸は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］

[In the general formula (5), A ¹ independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁵⁷ or -COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In A ¹ , the "substituent" of the phenyl group which may have a substituent and the "substituent" of the heterocyclic group which may have a substituent are the "substituent" in A of the general formula (4). Is the same as.

The alkyl group having 1 to 4 carbon atoms in R ⁵¹ , R ⁵⁷ , and R ⁵⁸ may be linear or branched, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, or a butyl group. , Isobutyl group, sec-butyl group, tert-butyl group.

As the pigment, from the viewpoint of lightness, A ¹ is preferably a phenyl group which may have a substituent. Further, from the viewpoint of lightness and dispersibility, it is preferred that R ⁵¹ is an alkyl group or -OR ⁵⁷ of 1 to 4 carbon atoms, more preferably R ⁵¹ is a methyl group or a methoxy group.

The colorant used in the present invention may have a chemical structure of the general formula (5) or a homovariant thereof, or may be a pigment having any crystal morphology, and may be any so-called polymorph. It may be a mixed crystal of pigments having a crystal morphology. The crystal morphology of these pigments can be confirmed by powder X-ray diffraction measurement and X-ray crystal structure analysis.

Examples of the naphthol azo pigment represented by the general formula (5) include C.I. I. Pigment Red 176 and the like.

［一般式（３）中、Ｚ₁〜Ｚ₁₃は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシル基、置換基を有してもよいアリール基、−ＳＯ₃Ｈ、−ＣＯＯＨ、およびこれら酸性基の１価〜３価の金属塩、アルキルアンモニウム塩、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルファモイル基を示す。
Ｚ₁〜Ｚ₄、および／または、Ｚ₁₀〜Ｚ₁₃の隣接した基は、一体となって、置換基を有してもよい芳香環を形成する場合がある。 As the quinophthalone pigment, the quinophthalone compound represented by the general formula (3) is preferable.

[In the general formula (3), Z _{1 to} Z ₁₃ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The sulfamoyl group which may have is shown.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may together form an aromatic ring that may have a substituent.

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group and an n-octyl group. In addition to a linear or branched alkyl group such as a group, a stearyl group and a 2-ethylhexyl group, a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group and a 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4- Examples thereof include an alkyl group having a substituent such as a methoxybenzyl group, a 4-nitrobenzyl group and a 2,4-dichlorobenzyl group.

Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a few. -In addition to linear or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy group, n-octyloxy group, stearyloxy group and 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2 , 2,2-Trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy Examples thereof include an alkoxyl group having a substituent such as a group and a benzyloxy group.

The aryl group which may have a substituent includes an aryl group such as a phenyl group, a naphthyl group and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group and a p-. Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-Trichloro-2-naphthyl group, anthraquinonyl group, 2-aminoanthraquinonyl group and other aryl groups having substituents can be mentioned.

As the acidic _group, -SO 3 H, -COOH, and examples of the monovalent to trivalent metal salt thereof acidic groups, sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts And so on. Examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, and quaternary alkyls such as palmityltrimethylammonium, dilauryldimethylammonium and distealyldimethylammonium salts. Ammonium salt can be mentioned.

"Substituents" in the phthalimidemethyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ −) which may have a substituent and the sulfamoyl group (H ₂ NSO ₂ −) which may have a substituent. Examples thereof include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent and the like.

_{Adjacent groups of Z 1 to} Z ₄ and / or Z _{10 to} Z ₁₃ of the general formula (3) may be integrated to form an aromatic ring which may have a substituent. Examples of the aromatic ring here include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and the heteroaromatic ring includes pyridine. Examples thereof include a ring, a pyrazine ring, a pyrrol ring, a quinoline ring, a quinoxalin ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for a color filter of the present invention include the quinophthalone compounds (a) to (r) shown below, and the present invention includes these. Not limited. Further, the quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited thereto.

Pigments other than the above include, for example, C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 95, 112, 114, 119, 122, 136, 144, 146, 164, 166, 168, 169, 170, 171, 175, 177, 178, 179, 184, 187, 185, 200, 202, 208, 210, 213, 214, 220, 221, 242, 246, 253, 254, 255, 256, 258, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, C.I. I. Pigmen Orange 1, 4, 15, 16, 22, 24, 38, 43, 71, 73, 74, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,49,53,55,60,61,62,63,65,73,74,75,77,81,83,87,93,94, 95, 97, 98, 100, 101, 104, 105, 106, 108, 109, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124, 126, 127, 128, 129, 130, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 205, 214, 213, 218, 219, 220, 221 and the like can also be preferably used. Above all, C.I. I. Pigment Red 176, 177, 254, 242, C.I. I. Pigment Yellow 138, 139, 150, 185 are preferred, and particularly preferred colorants are C.I. I. Pigment Yellow 139.

Further, as the dye, a xanthene type, an azo type (pyridone type, barbituric acid type, metal complex type, etc.), a disazo type, an anthraquinone type, or the like may be used in combination. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338.

When a colorant other than the azo pigment [A] represented by the general formula (1) or (2) is used in combination with the colorant of the present invention, the azo of the present invention is used in the total amount of the colorant (100% by mass). The pigment [A] is preferably in the range of 20 to 100% by mass. More preferably, it is in the range of 30 to 100% by mass. When the azo pigment [A] is 20% by mass or more, it is preferable because an excellent effect of lightness can be sufficiently exhibited.

(Miniaturization of colorants)
The pigment used in the present invention can be miniaturized and used. The azo pigment [A] is also preferably used after being miniaturized, but the miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used and are exemplified in the present invention. As described above, the salt milling treatment by the kneader method, which is a kind of wet grinding, can be performed.
By miniaturizing it, it can be suitably used as a red coloring composition for an organic EL display device.

The primary particle size of the finely divided pigment is preferably 20 nm or more because the dispersion in the colorant carrier is good. Further, since it is possible to form a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferable range is the range of 25 to 85 nm.
The primary particle size of the pigment was determined by a method of directly measuring the size of the primary particle from an electron micrograph of the pigment by a TEM (transmission electron microscope). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having a obtained particle size to obtain an average volume, and the length of one side of the cube having this average volume is the average primary. The particle size.

In the salt milling treatment, a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is heated using a kneader such as a kneader, a trimix, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. This is a treatment in which the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment.

The water-soluble organic solvent has a function of wetting the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

<Binder resin>
The binder resin is for dispersing, dyeing, or permeating a colorant, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to the heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of colorant components in the developing process.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

When the binder resin is used as a photosensitive coloring composition for a color filter, a carboxyl group that acts as a colorant adsorbent group and an alkali-soluble group during development, an aliphatic group that acts as an affinity group for a colorant carrier and a solvent, and an aliphatic group. The balance of aromatic groups is important for the dispersibility, permeability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by mass or less.

Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (i) and (ii) shown below.

[Method (i)]
As the method (i), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other types of monomers can be used. , An unsaturated monobasic acid carboxyl group having an unsaturated ethylenic double bond is added and reacted, and a polybasic acid anhydride is reacted with the generated hydroxyl group to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4 epoxybutyl (meth) acrylate. And 3,4 epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. From the viewpoint of reactivity with unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferable.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride may be used to obtain the remaining anhydride. It is also possible to hydrolyze the group. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further increased.

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method of adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and by copolymerizing with another unsaturated monobasic acid monomer having a carboxyl group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylates to which (poly) 12-hydroxystearic acid and the like are added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

[Thermosetting compound]
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a binder resin.

Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins. Examples include, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin.

Examples of the monomer and oligomer that cure with ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Ether Di (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.
These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The content of the photopolymerizable monomer is preferably 1 to 600 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 500 parts by mass from the viewpoint of photocurability and developability. ..

<Photopolymerization initiator [B]>
The photosensitive coloring composition of the present invention contains the photopolymerization initiator [B], so that the composition can be cured by ultraviolet irradiation and a filter segment can be formed by a photolithography method. It can be prepared in the form of a type photosensitive coloring composition. Above all, by containing the oxime ester-based photopolymerization initiator [B1], a photosensitive coloring composition having good color characteristics, excellent heat resistance, and good patterning properties can be obtained.

(Oxime ester compound [B1])
The oxime ester-based photopolymerization initiator [B1] breaks the NO bond of oxime by absorbing ultraviolet rays, and produces iminyl radicals and alkiloxi radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. More preferably, when it has a carbazole group, it can be a composition having excellent lightness and color purity. Particularly preferred is an oxime ester-based photopolymerization initiator represented by the general formula (6).

一般式（６）において、
Ｙ¹は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アシルオキシ基、アミノ基、ホスフィノイル基、カルバモイル基、もしくはスルファモイル基であり、
Ｙ²は、水素原子、または置換基を有しても良い、アルケニル基、アルキル基、アルキルオキシ基、アリール基、アリールオキシ基、複素環基、複素環オキシ基、アルキルスルファニル基、アリールスルファニル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基アシルオキシ基、もしくはアミノ基である。
Ｚは、直接結合又は−ＣＯ−基、
Ｙ³は、置換基を有しても良いカルバゾール基を含む１価の有機基、Ｐｈ−Ｓ−Ｐｈ−基（Ｐｈは、置換基を有しても良い、フェニル基又はフェニレン基を示す）等であることが好ましい。 (Oxime ester-based photopolymerization initiator represented by the general formula (6))

In the general formula (6)
Y ¹ may have a hydrogen atom or a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group. , Alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group.
Y ² may have a hydrogen atom or a substituent, an alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group. , Alkyl sulphinyl group, aryl sulphinyl group, alkyl sulfonyl group, aryl sulfonyl group acyloxy group, or amino group.
Z is a direct bond or -CO- group,
Y ³ is a monovalent organic group containing a carbazole group which may have a substituent, Ph-S-Ph- group (Ph indicates a phenyl group or a phenylene group which may have a substituent). Etc. are preferable.

Examples of the ^{alkenyl group which may have a substituent in Y 1} include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, which have a plurality of carbons in the structure. -It may have a carbon double bond, and specific examples thereof include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, and a 1-pentenyl group. , 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1 , 3-Butadienyl group, cyclohexadienyl group, cyclopentadienyl group and the like can be mentioned, but the present invention is not limited thereto.

The alkyl group which may have a substituent in Y ¹ is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms, and optionally 1 Included are linear, branched, monocyclic or condensed polycyclic alkyl groups interrupted by more than one —O—. Specific examples of linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of linear and branched alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- are -CH ₂ -O-CH ₃ and -CH _2. −CH ₂ −O−CH ₂ −CH ₃ , −CH ₂ −CH ₂ −CH ₂ −O−CH ₂ −CH ₃ , − (CH ₂ −CH ₂ −O) _n −CH ₃ (where n is 1 From 8), − (CH ₂ −CH ₂ −CH ₂ −O) _m −CH ₃ (where m is 1 to 5), _{−CH 2} −CH (CH ₃ ) −O−CH ₂ − CH ₃ −, −CH ₂ −CH− (OCH ₃ ) _2, etc. can be mentioned, but the present invention is not limited thereto.

Specific examples of monocyclic or condensed polycyclic alkyl groups having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include, but are limited to: It is not something that will be done.

The ^{alkyloxy group which may have a substituent in Y 1} is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms. Included are linear, branched, monocyclic or condensed polycyclic alkyloxy groups optionally interrupted by one or more —O—s. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy groups having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group and hexyloxy. Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group , 4-Decilcyclohexyloxy group and the like can be mentioned, but the present invention is not limited thereto. Specific examples of linear and branched alkyloxy groups having 2 to 18 carbon atoms and optionally interrupted by one or more -O- are -O-CH ₂ -O-CH ₃ , −O−CH ₂ −CH ₂ −O−CH ₂ −CH ₃ , −O−CH ₂ −CH ₂ −CH ₂ −O−CH ₂ −CH ₃ , −O− (CH ₂ −CH ₂ −O) _n −CH ₃ (where n is 1 to 8), −O− (CH ₂ −CH ₂ −CH ₂ −O) _m −CH ₃ (where m is 1 to 5), −O−CH _{2 -CH (CH 3) -O-} CH 2 -CH 3 -, - OCH 2 -CH- (OCH 3) can be cited _2, etc., but is not limited thereto.

Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and optionally interrupted by one or more of -O- include the following. Not limited.

Examples of the aryl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms, and specific examples thereof include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Group, 1-anthrill group, 9-anthrill group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthril group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl Group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-kisilyl group, 2,5-kissyl group, mesityl group, p. -Cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, Examples thereof include, but are not limited to, an o-mercaptophenyl group, a p-cyanophenyl group, an m-nitrophenyl group, and an m-azidophenyl group.

Examples of the aryloxy group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms, and specific examples thereof include a phenoxy group, a naphthyloxy group, and 2-. Naftyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group , 9-Fluorenyloxy group and the like, but are not limited thereto.

Examples of the heterocyclic group which may have a substituent in Y ¹ include aromatic or aliphatic heterocyclic groups having 4 to 24 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. , 2-thienyl group, 2-benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl Group, chromenyl group, xanthenyl group, phenoxatyynyl group, 2H-pyrrylyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridadinyl group, indridinyl group, isoindrill group, 3H-indrill group , 2-Indolyl group, 3-Indrill group, 1H-Indazolyl group, Prinyl group, 4H-Kinolidinyl group, Isoquinolyl group, Kinolyl group, Phthalazinyl group, Naftyridinyl group, Kinoxanyryl group, Kinazolinyl group, Synnolinyl group, Pteridinyl group, 4aH- Carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbazolyl group, phenanthridinyl group, 2-acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group. , Isoxazolyl group, Frazanyl group, 3-Phenixazinyl group, Isochromanyl group, Chromanyl group, Pyrrolidinyl group, Pyrrolinyl group, Imidazolidinyl group, Imidazolinyl group, Pyrazolydinyl group, Pyrazolinyl group, Piperidyl group, Piperazinyl group, Indolinyl group, Isoindrinyl group. , Morphorinyl group, thioxanthril group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxatyynyl group, 3-cummarinyl group and the like, but are limited thereto. It's not a thing.

Examples of the ^{heterocyclic oxy group which may have a substituent in Y 1} include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms including a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom. Specific examples thereof include 2-furanyloxy group, 2-thienyloxy group, 2-indrilloxy group, 3-indrilloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group and 2-carbazoli. Examples thereof include, but are not limited to, a luoxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

Examples of the alkylsulfanyl group which may have a substituent in Y ¹ include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples thereof include a methylthio group. , Ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like, but are not limited thereto.

Examples of the arylsulfanyl group which may have a substituent in Y ¹ include a monocyclic or condensed polycyclic arylthio group having 6 to 18 carbon atoms, and specific examples thereof include a phenylthio group, a 1-naphthylthio group and a 2-. Examples thereof include, but are not limited to, a naphthylthio group, a 9-anthrylthio group, a 9-phenanthrylthio group, and the like.

As the ^{alkylsulfinyl group which may have a substituent in Y 1} , an alkylsulfinyl group having 1 to 20 carbon atoms is preferable, and specific examples thereof include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group and an isopropylsulfinyl group. Butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methyloxymethylsulfinyl group, etc. However, it is not limited to these.

As the ^{arylsulfinyl group which may have a substituent in Y 1,} an arylsulfinyl group having 6 to 30 carbon atoms is preferable, and specific examples thereof include a phenylsulfinyl group, a 1-naphthylsulfinyl group and a 2-naphthylsulfinyl group. 2-Chlorophenyl sulfinyl group, 2-methylphenyl sulfinyl group, 2-methyloxyphenyl sulfinyl group, 2-butyloxyphenyl sulfinyl group, 3-chlorophenyl sulfinyl group, 3-trifluoromethylphenyl sulfinyl group, 3-cyanophenyl sulfinyl group , 3-Nitrophenyl Sulfinyl Group, 4-Fluorophenyl Sulfinyl Group, 4-Cyanophenyl Sulfinyl Group, 4-Methyloxyphenyl Sulfinyl Group, 4-Methyl Sulfanylphenyl Sulfinyl Group, 4-Phenyl Sulfanylphenyl Sulfinyl Group, 4-Dimethylamino Examples thereof include, but are not limited to, a phenylsulfinyl group.

The alkylsulfonyl group which may have a substituent in Y ¹ is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and specific examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, and an isopropylsulfonyl group. Butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoyylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, etc. However, it is not limited to these.

The ^{arylsulfonyl group which may have a substituent in Y 1} is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and specific examples thereof include a phenylsulfonyl group, a 1-naphthylsulfonyl group, and a 2-naphthylsulfonyl group. 2-Chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group , 3-Nitrophenylsulfonyl Group, 4-Fluorophenylsulfonyl Group, 4-Cyanophenylsulfonyl Group, 4-Methyloxyphenylsulfonyl Group, 4-Methylsulfanylphenylsulfonyl Group, 4-Phenylsulfanylphenylsulfonyl Group, 4-Dimethylamino Examples thereof include, but are not limited to, phenylsulfonyl groups.

Examples of the acyl group which may have a substituent in Y ¹ include a hydrogen atom, a carbonyl group in which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, and a carbon number of carbon atoms. A carbonyl group substituted with an alkyloxy group of 2 to 20, a carbonyl group to which a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms is bonded, and a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms are present. Examples thereof include a carbonyl group in which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms including a substituted carbonyl group, a nitrogen atom, an oxygen atom, a sulfur atom and a phosphorus atom is bonded, and specific examples thereof include formyl. Group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyle Group, isoclotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyl Oxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoil group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitro Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrryloxycarbonyl group, 3-fluoroyl Groups, 2-tenoyl groups, nicotinoyle groups, isonicotinoyl groups and the like can be mentioned, but are not limited thereto.

Examples of the acyloxy group which may have a substituent in Y ¹ include an acyloxy group having 2 to 20 carbon atoms, and specific examples thereof include an acetyloxy group, a propanoyloxy group, a butanoyloxy group, and a pentanoyloxy group. Examples thereof include a group, a trifluoromethylcarbonyloxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, a 2-naphthylcarbonyloxy group and the like.

Examples ^{of the amino group which may have a substituent in Y 1} include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, a dibenzylamino group and the like. Can be mentioned.

Here, as the alkylamino group, a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group and a dodecylamino group. , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Examples thereof include an amino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentylamino group, a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, a 2-adamantamino group and the like. , Not limited to these.

Examples of the dialkylamino group include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group and didodecylamino group. Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples thereof include, but are not limited to, piperadino groups.

Examples of the arylamino group include anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group and 4-. Examples thereof include, but are not limited to, a biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditrilamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group and N. Examples thereof include, but are not limited to, an ethylanilino group and an N-methyl-1-naphthylamino group.

Examples of the phosphinoyl group which may have a substituent in Y ¹ include a phosphinoyl group having 2 to 50 carbon atoms, and specific examples thereof include a dimethylphosphinoyl group, a diethylphosphinoyl group, and a dipropylphosphinoyl. Examples include, but are limited to, a group, a diphenylphosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, a dibenzoylphosphinoyl group, a bis (2,4,6-trimethylphenyl) phosphinoyl group and the like. It is not something that is done.

Examples of the carbamoyl group which may have a substituent in Y ¹ include a carbamoyl group having 1 to 30 carbon atoms, and specific examples thereof include an N-methylcarbamoyl group, an N-ethylcarbamoyl group and an N-propylcarbamoyl group. , N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group. Group, N-2-chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl Examples thereof include, but are not limited to, -N-phenylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

Examples of the sulfamoyl group which may have a substituent in Y ¹ include a sulfamoyl group having 0 to 30 carbon atoms, and specific examples thereof include a sulfamoyl group, an N-alkyl sulfamoyl group, and an N-aryl sulfamoyl. Examples include groups, N, N-dialkylsulfamoyl groups, N, N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamooil groups and the like. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsul. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenyl sulfamoyl group, N-2-chlorophenyl sulfamoyl group, N-2-methoxyphenyl sulfamoyl group, N-2-isopropoxyphenyl sulfamoyl group, N-3-chlorophenyl sulfamoyl group, N-3-nitrophenyl sulfamoyl group, N-3-cyanophenyl sulfamoyl group, N-4-methoxyphenyl sulfamoyl group, N-4-cyanophenyl sulfamoyl group, N-4-dimethylamino Phenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl Examples thereof include, but are not limited to, a group, an N, N-dibutylsulfamoyl group, an N, N-diphenylsulfamoyl group and the like.

An alkenyl group, an alkyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, which may have a substituent in ^{Y 2,} As the arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, and amino group, the above-mentioned alkenyl group which may have a substituent in R1, an alkyl group which may have a substituent, and a substituent may be used. It has an alkyloxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, a heterocyclic group which may have a substituent, and a substituent. Also good heterocyclic oxy group, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkylsulfinyl group which may have a substituent, and may have a substituent. It may have a good arylsulfinyl group, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyloxy group which may have a substituent, and a substituent. Synonymous with amino group.

Examples of these substituents in Y ¹ and Y ² include a halogen group such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group, a phenoxy group and a p-tolyloxy. Aryloxy group such as an aryloxy group, a methoxycarbonyl group, a butoxycarbonyl group, an alkoxycarbonyl group such as a phenoxycarbonyl group, an acyloxy group such as an acetoxy group, a propionyloxy group and a benzoyloxy group, an acetyl group, a benzoyl group, an isobutyryl group and an acryloyl group. , Acyl group such as methacryloyl group, metoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group and p-tolylsulfanyl group, methylamino group, cyclohexylamino group and the like. Dialkylamino groups such as alkylamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino group such as phenylamino group and p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group and other alkyl groups, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl In addition to aryl groups such as groups, furyl groups, heterocyclic groups such as thienyl groups, hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups, p-toluenesulfonyl groups, amino groups, nitro groups, Examples thereof include a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group.
Further, one or more or one or more of these substituents may be present, and the hydrogen atom of these substituents may be further substituted with another substituent.

Among these, the oxime ester-based photopolymerization initiator represented by the following general formula (7) or (8) is excellent in sensitivity and is preferable.

[Oxime ester-based photopolymerization initiator represented by the general formula (7)]

The general formula (7) corresponds to the case where Z is a -CO- group and Y ³ is a Ph-S-Ph- group in the ^{general formula (6), and Y 4 to Y 6} are hydrogen atoms or substituents. An alkyl group or an aryl group which may have an alkyl group or an aryl group is preferable.

Further, Y ¹ is preferably an aryl group which may have a substituent, Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and Y ^{4 to Y 6} is preferably a hydrogen atom. ..

The alkyl group which may have a substituent or the aryl group which may have a substituent in ^{Y 4 to Y 6} is synonymous with the alkyl group or the aryl group in ^{Y 1} and Y ^2.

The substituent of the alkyl group which may have a substituent or the aryl group which may have a substituent is synonymous with the substituent in ^{Y 1} and Y ^2.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. It is a cycloalkyl group such as a cyclooctadecyl group.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (7) include a photopolymerization initiator represented by the following chemical formula (7-1) or (7-2).

[Oxime ester-based photopolymerization initiator represented by the general formula (8)]

^{The general formula (8) corresponds to the case where Y 3} in the general formula (6) is a monovalent organic group containing a carbazole group which may have a substituent, and Y ^{7 to Y 14} are Y ¹ and Y. It is synonymous with the substituent in ^2.

Further, the alkyl group having 1 to 20 carbon atoms which may have a substituent as ^{Y 1 may have an alkyl group having 1 to 20 carbon atoms which may have a substituent as Y 2} , or may have a substituent. A good aryl group is ^{preferably an alkyl group having a hydrogen atom as Y 7 to Y 14} , or an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent.

When Z in the general formula (8) is a direct bond, an oxime ester-based photopolymerization initiator represented by the following general formula (8a) is preferable.

"Oxime ester-based photopolymerization initiator represented by the general formula (8a)"

The general formula (8a) corresponds to the case of a monovalent organic group containing a carbazole group in which Z is a direct bond and Y ³ may have a substituent in the general formula (8), and is in the general formula (8). Y ^{7 to Y 10} and Y ^{12 to Y 13} are hydrogen atoms.
Further, Y ¹¹ is ^{preferably a Y 15-} CO- group or a nitro group. Y ¹⁵ is ^{synonymous with the substituents in Y 1} and Y ² , and is preferably an aryl group which may have a substituent. The Y ^15- CO- group is preferably an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, or a metoxalyl group which may further have a substituent. More preferably, it is a benzoyl group or a nitro group which may have a substituent. As Y ¹⁴ , an alkyl group having 1 to 20 carbon atoms which may have a substituent or an aryl group which may have a substituent is preferable.

Further, as the substituent in the benzoyl group which may have a substituent, an alkyl group having 1 to 20 carbon atoms or an alkyloxy group is preferable. Further, as the alkyl group, a methyl group and an ethyl group are preferable, and among the alkyloxy groups, a linear or branched chain having 2 to 18 carbon atoms and optionally interrupted by one or more —O—. Monocyclic or condensed polycyclic alkyloxy groups are preferred, with ^{linear, branched, monocyclic or condensed polycyclic groups having 2 to 18 carbon atoms in Y 1} and optionally interrupted by one or more —O—s. Synonymous with alkyloxy group.

Y ² is preferably an alkyl group having 1 to 20 carbon atoms which may have a substituent, and is preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, etc. It is a cycloalkyl group such as a cyclooctadecyl group. Further, an aryl group which may have a substituent is preferable, and an alkyl group having 1 to 20 carbon atoms which may further have a substituent, or a methoxy group, an ethoxy group, or a tert-butoxy group is preferable as the substituent. Alkoxy groups such as are preferable.

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (8a) are photopolymerization initiators represented by the following chemical formulas (8a-1) to (8a-4).

"Oxime ester-based photopolymerization initiator represented by the general formula (8b)"
When Z in the general formula (8) is a −CO— group, an oxime ester-based photopolymerization initiator represented by the following general formula (8b) is preferable.

The general formula (8b) corresponds to the case of a monovalent organic group containing a carbazole group in which Z may have a —CO— group and Y ^{3 may have a substituent in the general formula (5), and is a keto-type carbazole group.} It is an oxime ester-based photopolymerization initiator having the above.
Y ^{7 to Y 13} are preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a ^{substituent, and Y 14} may have a substituent. It is preferably a good aryl group.
As the substituent of the aryl group which may have a substituent, an acyl group such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group and a metoxalyl group is preferable, and a benzoyl group is more preferable.

この他に、下記化学式（９−１）、（９−２）で表されるオキシムエステル系光重合開始剤も好適に用いることができる。

Specific examples of the oxime ester-based photopolymerization initiator represented by the general formula (8b) are photopolymerization initiators represented by the following chemical formulas (8b-1) to (8b-4).

In addition to this, oxime ester-based photopolymerization initiators represented by the following chemical formulas (9-1) and (9-2) can also be preferably used.

Commercially available products of these oxime ester-based photopolymerization initiators [B1] are 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)] (IRGACURE) from BASF. OXE-01), Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (IRGACURE OXE 02) is commercially available. There is. In addition, the oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-02998, etc. It is also possible to use an ester-based photopolymerization initiator.
(Other photopolymerization initiators)
The red coloring composition for an organic EL display device of the present invention may contain other photopolymerization initiators in addition to the oxime ester-based photopolymerization initiator [B1].
Examples of the other photopolymerization initiator [B2] in the present invention include acetphenone-based compounds, benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, triazine-based compounds, phosphine-based compounds, quinone-based compounds, borate-based compounds, and carbazole-based compounds. , An imidazole-based compound, a photopolymerization initiator such as a titanosen-based compound, and a sensitizer [B3].

Specifically, as the photopolymerization initiator [B2], 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane- 1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methyl) Acetphenone such as phenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one Systems Compounds; Benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, Benzophenone compounds such as 4-benzoyl-4'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, Thioxanthone compounds such as isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s -Triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- Piperonil-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine , Or triazine compounds such as 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; bis (2,4,6-trimethylbenzoyl) phenylphosphine. Oxides or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds. Compound; Alternatively, a titanosen-based compound or the like can be mentioned.

Examples of the sensitizer [B3] include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acridin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrilium derivative, tetraphyllin derivative, anurene derivative, spiropyran derivative, spiroxazine derivative, thiospiropirane derivative, metal arene complex, organic ruthenium complex, or michiller ketone derivative, biimidazole. Derivatives, α-acyloxyester, acylphosphine oxide, methylphenylglycilate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', Or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Among other photopolymerization initiators, since the patterning property is good, the photopolymerization initiator [B2] is an acetophenone-based compound, a phosphine-based compound, and an imidazole-based compound, and the sensitizer [B3] is a thioxanthone derivative. It is preferable to use a Michler ketone derivative, a carbazole derivative or the like.

As the photopolymerization initiator such as the photopolymerization initiator [B1], [B2], or the sensitizer [B3], one type may be used alone, or two or more types may be mixed at an arbitrary ratio as required. Can be done.

The content of the photopolymerization initiator [B] is preferably 0.01 to 200 parts by mass with respect to 100 parts by mass of the colorant, and is 0.1 to 150 parts by mass from the viewpoint of photocurability and developability. It is more preferable to have.

The mass ratio of the photopolymerization initiator [B] to the photopolymerizable monomer (photopolymerization initiator [B]) / (photopolymerizable monomer) in the red coloring composition for an organic EL display device of the present invention is It is preferably 0.01 to 3.00, and more preferably 0.04 to 2.50, because both photocurability and resolution can be achieved.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and the colored film is applied onto a substrate such as a glass substrate so as to have a dry film thickness of 0.2 to 5 μm to form a colored film. It is preferable to contain an organic solvent to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone and 2-methyl-. 1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propylacetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, Isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether Acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, Dipropylene glycol mono Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propyl acetate, dibasic acid ester and the like.
These solvents can be used alone or in admixture of two or more at any ratio, if necessary.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl have good dispersibility, permeability, and coatability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a coloring film having a desired uniform film thickness, the amount is 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant. It is preferable to use it.

<Antioxidant>
The red coloring composition for an organic EL display device of the present invention can contain an antioxidant. The antioxidant is a coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the red coloring composition for an organic EL display device from being oxidized and yellowing due to the thermal process at the time of thermosetting or ITO annealing. The permeability of the material can be increased. Therefore, by containing an antioxidant, it is possible to prevent yellowing due to oxidation during the heating step and obtain a high transmittance of the coating film.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposition function, and specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Further, the antioxidant used in the present invention preferably does not contain a halogen atom.

Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants or sulfur-based antioxidants. Agents are mentioned. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), and the like. 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di) -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-t-butyl-5-methylphenol), 2,2'-thio- Bis- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2'thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) )-Propionate, 1,1,3-Tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 2,2'-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro) Phenol) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

Examples of the hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate. N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like. In addition, oligomer-type and polymer-type compounds having a hindered amine structure can also be used.

Phenyl antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenylisodecyl. Phenylphosphite, diphenyltridecylphosphite, triphenylphosphite, tris (nonylphenyl) phosphite, 4,4'isopropyridendiphenol alkylphosphite, trisnonylphenylphosphite, trisdinonylphenylphosphite, tris (2) , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonyl) Phenyl) Pentaerythritol diphosphite, Phenylbisphenol A Pentaerythritol diphosphite, Tetratridecyl 4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, Hexatridecyl 1,1,3- Tris (2-methyl-4-hydroxy-5-t-butylphenyl) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis (4-t-butylphenyl) Phosphite, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2, 4-Ditert-butyl-6-methylphenyl) and the like. In addition, oligomer-type and polymer-type compounds having a phosphite structure can also be used.

Examples of sulfur-based antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]-. Examples thereof include o-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol. In addition, oligomer-type and polymer-type compounds having a thioether structure can also be used.

As the benzotriazole-based antioxidant, an oligomer-type compound and a polymer-type compound having a benzotriazole structure can be used.

Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-. Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2- Examples thereof include hydroxy-4-methoxy-5 sulfobenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. In addition, oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

Examples of the triazine-based antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

Examples of the salicylic acid ester-based antioxidant include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate. In addition, oligomer-type and polymer-type compounds having a sulcylic acid ester structure can also be used.

These antioxidants can be used alone or in admixture of two or more at any ratio as required.

Further, the content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content mass of the red coloring composition because the spectral characteristics and the sensitivity are good.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.

Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the red coloring composition for an organic EL display device of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning Co., Ltd., BYK-333 manufactured by Big Chemie Co., Ltd., and the like. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by Big Chemie. Didimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by mass based on 100% by mass of the total mass of the coloring composition.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

The binding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are repeatedly bonded alternately. Didimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. 2207, but is not limited to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalline sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as an auxiliary to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as an auxiliary to the leveling agent include ether types such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether and polyoxyethylene nonylphenyl ether, alkyl betaine such as alkyldimethylaminoacetic acid betaine, and alkylimidazolin. Examples thereof include amphoteric surfactants such as, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. As the curing agent, a phenol-based resin, an amine-based compound, an acid anhydride, an active ester, a carboxylic acid-based compound, a sulfonic acid-based compound, and the like are effective, but the curing agent is not particularly limited thereto, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl). -4-Methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methyl imidazole, etc.), phosphorus compounds (eg, tri) Phenylphosphin, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2, etc.) 4-Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting resin.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. Further, an adhesion improving agent such as a silane coupling agent can be contained in order to improve the adhesion to the transparent substrate.

(Storage stabilizer)
Examples of the storage stabilizer include organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

(Adhesion improver)
Examples of the adhesion improver include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β- (3,). 4-Epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino) Ethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

(Polyfunctional thiol)
The coloring composition of the present invention may contain a compound having two or more thiol (SH) groups as a polyfunctional thiol.
By using a polyfunctional thiol together with a photopolymerization initiator, a chain transfer agent acts as a chain transfer agent in the radical polymerization process after light irradiation, and a chile radical that is less susceptible to polymerization inhibition by oxygen is generated, so that the obtained coloring composition has high sensitivity. It becomes. In particular, polyfunctional aliphatic thiols in which the SH group is bonded to an aliphatic group such as methylene or ethylene group are preferable. Examples of the polyfunctional thiol include hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropio. Nate, Trimethylol Propanetristhioglycolate, Trimethylol Protantithithiopropionate, Trimethylol Propanthris (3-mercaptobutyrate), Pentaerythritol Tetrakissthioglycolate, Pentaerythritol Terrakis (3-Mercaptopropionate) , Tris-trimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6 -Dimercapto-s-triazine and the like can be mentioned, with preference given to ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, pentaerythritol terakis (3-mercaptopropionate) and the like.

These polyfunctional thiols can be used alone or in admixture of two or more.
The content of the polyfunctional thiol is preferably 0.05 to 100 parts by mass, more preferably 0.10 to 50.0 parts by mass with respect to 100 parts by mass of the colorant. If the content of the polyfunctional thiol is less than 0.05 parts by mass, the effect of the chain transfer agent is small, and if it is more than 100 parts by mass, the polymerization initiation function is not improved, and the developability, adhesion, etc. are insufficient. ..

<Manufacturing method of coloring composition>
The coloring composition of the present invention comprises a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a colorant in a colorant carrier such as a binder resin and / or a solvent, preferably a dispersion aid. It can be finely dispersed and produced by using various dispersion means such as a vertical sand mill, an annual bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants may be dispersed in the colorant carrier at the same time, or separately dispersed in the colorant carrier may be mixed.
If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing it as described above. No need.

When used as a photosensitive coloring composition (resist material) for an organic EL display device, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition comprises the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the dye carrier, a dispersion aid such as a resin-type dispersant, a dye derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high brightness and viscosity stability. Become good.

[Resin type dispersant]
The resin-type dispersant has a colorant-affinitive moiety having a property of adsorbing to the additive colorant and a moiety compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamidophosphate, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oily dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.
Further, the resin type dispersant may have an oxetane group. Since the resin-type dispersant has an oxetane group, the colored composition containing the dispersant has excellent heat resistance after curing.

As the dispersant used in the present invention, a polymer dispersant having a basic functional group is preferable, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, and a nitrogen-containing heterocycle. A nitrogen atom-containing acrylic block copolymer and a urethane-based polymer dispersant having a functional group containing the above are preferable. The resin type dispersant is preferably used in an amount of about 1 to 200% by mass with respect to the total amount of the colorant, and more preferably about 5 to 100% by mass from the viewpoint of film forming property.

Examples of commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemie Japan. 167,168,170,171,174,180,181,182,183,184,185,190,2000,2001,2009,2010,2020,2025,2050,2070, 2095,2150,2155,2163,2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc. 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF. 4,300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno's Ajispa-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

Further, the resin-type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin-type dispersant having a carboxyl group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A resin-type dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP-A-2008-029901, and JP-A-2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the number of hydroxyl groups at the terminal is plural, the compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained therein. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product between the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but if the reaction conditions are the same as those of the raw material, the same can be theoretically obtained.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalline sulfonate, sodium alkyldiphenyl ether disulfonate. , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazolin, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the resin type dispersant and the surfactant are added, the blending amount is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the blending amount of the resin type dispersant and the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect, and when the blending amount is more than 55 parts by mass, the dispersion is adversely affected by the excessive dispersant. May affect.

[Dye derivative]
A dye derivative can be added to the photosensitive coloring composition of the present invention, if necessary.
As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphoric acid group, an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or a phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl group.

Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments and benzo. Indole pigments such as isoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo, disazo, polyazo and other azo pigments, etc. Be done.
Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, Japanese Patent Laid-Open No. 2017-165820, Japanese Patent No. 5753266, and as an anthraquinone-based dye derivative, JP-A-63-246674. JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- JP-A-54128, JP-A-03-9961, JP-A-2000-273383, JP-A-2011-162662 as a dioxazine-based dye derivative, and JP-A-2007-314785 as a thiazineindigo-based dye derivative. Examples of JP-A and triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP-A-2006-291194, JP-A. 2008-31281, 2012-226110, naphthol-based dye derivatives, 2012-208329, 2014-5439, and azo-based dye derivatives, 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in Japanese Patent Laid-Open No. -181383, JP-A-2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.
These dye derivatives can be used alone or in combination of two or more.

From the viewpoint of improving dispersibility, the content of the dye derivative is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and most preferably 3 parts by mass or more with respect to 100 parts by mass of the colorant. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by mass or less, more preferably 35 parts by mass or less.

<Removal of coarse particles>
The colored composition of the present invention comprises coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration with a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not contain particles having a size of 0.5 μm or more. It is more preferably 0.3 μm or less.

<Color filter>
The color filter for an organic EL display device of the present invention will be described.
The color filter of the present invention comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, wherein the at least one red filter segment comprises the red coloring composition of the present invention. It is preferable to have.
Further, the green coloring composition forming the green filter segment can be produced in the same manner as the red coloring composition described above by replacing it with a green pigment or a dye. The same applies to the blue coloring composition forming the blue filter segment.

The green filter segment can be formed using a conventional green coloring composition. The green coloring composition is described in, for example, C.I. I. It is a composition obtained by using a green pigment such as Pigment Green 7, 10, 36, 37, 58, 59, 62 or 63. The green coloring composition includes C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, Yellow pigments such as 193, 194, 198, 199, 213, or 214 can be used in combination.

The blue filter segment can be formed using a conventional blue coloring composition containing a blue pigment and a colorant carrier. Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, or 64 and the like are used.

Further, the blue coloring composition includes C.I. I. Purple pigments such as Pigment Violet 23 and C.I. I. Metal lake pigments of rhodamine dyes such as Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a salt-forming compound of a basic dye or an acid dye exhibiting blue or purple can also be used.

_{The color filter for an organic EL display device of the present invention has peak wavelengths λ 1} and λ ₂ that maximize the emission intensity in a wavelength range of at least 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm, respectively, at a wavelength of λ ₁ . A colored film when a white organic EL light source having spectral characteristics in which the ratio (I ₂ / I ₁ ) of the emission intensity I _{2 to} the emission intensity I ₁ at the wavelength λ _{2 is 0.4 or more and 0.9 or less is used.} When the chromaticity coordinates in the XYZ color system are (xR, yR), (xG, yG), and (xB, yB), the area of the triangle surrounded by these three points is red (0.67, When it is 75% or more of the area surrounded by 0.33), green (0.21, 0.71), and blue (0.14, 0.08), the color reproducibility as a color display device is high. Therefore, it is preferable.

As the base material, a glass plate such as soda-lime glass, low-alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used. Further, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal display after the panelization.

<Manufacturing method of color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method using a coloring composition.

The formation of the colored film by the printing method can be patterned only by repeating printing and drying of the colored composition prepared as the printing ink, and therefore, it is low cost and excellent in mass productivity as a manufacturing method of the color filter. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and it is possible to adjust the ink viscosity with a dispersant or an extender pigment.

When forming a colored film by a photolithography method, a colored composition prepared as the solvent-developed or alkaline-developed colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution.
In order to increase the UV exposure sensitivity, the colored resist was applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin was applied and dried to form a film for preventing polymerization inhibition by oxygen. Later, UV exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above method, and the coloring composition of the present invention can be used in any method. The electrodeposition method is a method of manufacturing a color filter by electrodepositing and forming each color colored film on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a colored film is formed in advance on the surface of a peelable transfer base sheet, and the colored film is transferred to a desired substrate.

If a black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast of the display panel can be further enhanced. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the panel can be increased and the brightness can be improved.
An overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

<Organic EL display device>
The organic EL display device in the present invention contains an azo pigment [A] represented by the general formula (1) and / or (2), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator [B]. It is preferable that the display device has a color filter formed of the red coloring composition and a white light emitting organic EL element (hereinafter referred to as an organic EL element) as a light source.

(Organic EL element (white light emitting organic EL element))
_{The organic EL element used in the present invention has peak wavelengths λ 1} and λ ₂ that maximize the emission intensity in at least a wavelength range of 430 nm to 485 nm and a wavelength range of 560 nm to 620 nm, respectively, and emits light at a wavelength λ ₁ . It is preferable to have an emission spectrum in which the ratio (I ₂ / I ₁ ) of the emission intensity I _{2 at} the intensity I ₁ to the wavelength λ ₂ is 0.4 or more and 0.9 or less, and 0.5 or more and 0. It is more preferably 8 or less. Particularly preferably, it is 0.5 or more and 0.7 or less.
When the ratio of emission intensity I _{2 (I 2} / I ₁ ) has an emission spectrum of 0.4 or more and 0.9 or less, high brightness and wide color reproducibility can be obtained, which is preferable.

Further, it is preferable to have a maximum value of emission intensity or a shoulder in the wavelength range of 530 nm to 650 nm.
The wavelength range of 430 nm to 485 nm is preferable when a color display device including the color filter displays blue with good color reproducibility. More preferably, it is in the range of 430 nm to 475 nm.
By using an organic EL element satisfying these configurations and the color filter, it is possible to obtain a color display device having a wide color reproduction region and high brightness.

The organic EL element is composed of an element in which one or a plurality of organic layers are formed between an anode and a cathode. Here, the single-layer organic EL element refers to an element consisting of only a light-emitting layer between the anode and the cathode, while the multi-layer organic EL element refers to holes in the light-emitting layer in addition to the light-emitting layer. Hole injection layer, hole transport layer, hole blocking layer, electron injection for the purpose of facilitating electron injection and facilitating recombination of holes and electrons in the light emitting layer. Refers to a stack of layers and the like. Therefore, typical element configurations of the multilayer organic EL element are (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. , (3) anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Examples thereof include an element configuration in which layers are laminated such as an anode / a light emitting layer / a hole blocking layer / an electron injection layer / a cathode, and (8) an anode / a light emitting layer / an electron injection layer / a cathode. However, the organic EL element used in the present invention is not limited to these.

Further, each of the above-mentioned organic layers may be formed by a layer structure of two or more layers, or several layers may be repeatedly laminated. As such an example, in recent years, for the purpose of improving the light extraction efficiency, an element configuration called "multi-photon emission" in which a part of the layers of the above-mentioned multi-layer organic EL element is multi-layered has been proposed. This is, for example, in an organic EL element composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit. A method of laminating a plurality of layers of the portions can be mentioned.

First, the materials that can be used for each of these layers will be specifically exemplified. However, the materials that can be used in the present invention are not limited to these.

As a material that can be used for the hole injection layer, a phthalocyanine compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc) and the like can be used. In addition, there is also a material obtained by chemically doping a conductive polymer compound, and a material obtained by doping polyethylenedioxythiophene (abbreviation: PEDOT) with polystyrene sulphonic acid (abbreviation: PSS) or polyaniline (abbreviation: PANI) is used. You can also do it. In addition, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as _{aluminum oxide (abbreviation: Al 2} O _3). Ultra-thin films of the body are also effective. In addition, 4,4', 4''-tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4', 4''-tris [N- (3-methylphenyl) -N-phenyl-amino] -triphenylamine (abbreviation: MTDATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (Omitted: TPD), 4,4'-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4'-bis [N- (4- (4- (4) Aromatic amine compounds such as N, N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance exhibiting acceptability for these aromatic amine compounds may be added to the aromatic amine compound, specifically, 2,3,5,6-tetrafluoro-7 which is an acceptor for VOPc. , 7,8,8-Tetracyanoquinodimethane (abbreviation: F4-TCNQ) may be added, or α-NPD to which the acceptor MoO _x is added may be used.

As the material that can be used for the hole transport layer, an aromatic amine compound is suitable, and TDATA, MTDATA, TPD, α-NPD, DNTPD and the like described in the hole injection material can be used.

Examples of the electron transport material that can be used for the electron transport layer include tris (8-quinolinolat) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), and bis (10-hydroxybenzo). [H] -Kinolinato) berylium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenorato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola G] Zinc (abbreviation: Zn (BOX) ₂ ), bis [2- (2-hydroxyphenyl) benzothiazolato] zinc (abbreviation: Zn (BTZ) ₂ ) and other metal complexes can be mentioned. Furthermore, in addition to the metal complex, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- (P-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] Oxadiazole derivatives such as benzene (abbreviation: OXD-7), 3- (4-tert-butylphenyl) -4 -Phenyl-5- (4-biphenylyl) -1,2,4-triazole (abbreviation: TAZ), 3- (4-tert-butylphenyl) -4- (4-ethylphenyl) -5- (4-biphenylyl) ) -1,2,4-triazole (abbreviation: p-EtTA Z) and other triazole derivatives, 2,2', 2 "-(1,3,5-benzenetriyl) tris [1-phenyl-1H-benz" An imidazole derivative such as imidazole (abbreviation: TPBI), and a phenanthroline derivative such as vasofenantroline (abbreviation: BPhen) and vasocuproin (abbreviation: BCP) can be used.

Materials that can be used for the electron injection layer include Alq3, Almq3, BeBq2, BAlq, Zn (BOX) ₂ , Zn (BTZ) ₂ , PBD, OXD-7, TAZ, p-EtTAZ, and TPBI described above. Electron transport materials such as BPhen and BCP can be used. In addition, ultra-thin films of insulators such as alkali metal halides such as LiF and CsF, alkaline earth halides such as _{CaF 2 , and alkali metal oxides such as Li 2 O are often used.} Further, alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting donor properties with respect to these electron-injected materials may be added to the electron-injected material, and as the donor, an alkali metal, an alkaline earth metal, a rare earth metal, or the like can be used. Specifically, one in which lithium as a donor is added to BCP or one in which lithium as a donor is added to Alq ₃ can be used.

Further, as the hole blocking layer, a hole blocking material that can prevent holes that have passed through the light emitting layer from reaching the electron injection layer and can form a layer having excellent thin film forming properties is used. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinate) (4-phenylphenolate) aluminum and bis (2-methyl-8-hydroxyquinolina). -Gallium complex compounds such as (4-phenylphenylato) gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.

The light emitting layer that obtains white light emission is not particularly limited, and for example, the following can be used. That is, an element that defines the energy level of each layer of the organic EL laminated structure and emits light by using tunnel injection (European Patent No. 0390551), and a white light emitting element as an example of an element that also uses tunnel injection. A plurality of light emitting layers are described (Japanese Patent Laid-Open No. 3-230584), a light emitting layer having a two-layer structure (Japanese Patent Laid-Open No. 2-220390 and JP-A-2-216790), and a plurality of light emitting layers. A blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm) are laminated by being divided and composed of materials having different emission wavelengths (Japanese Patent Laid-Open No. 4-51491). Further, a structure containing a red fluorescent substance (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, the green light emitting layer has a region containing a red fluorescent dye, and further green fluorescence. Examples thereof include those having a structure containing a body (Japanese Patent Laid-Open No. 7-142169).

Further, as the light emitting material used in the present invention, a material known as a conventionally known light emitting material may be used. The following are examples of compounds preferably used for blue, green, orange to red emission. However, the light emitting material is not limited to the following concrete examples.

The blue emission is obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), a 9,10-diphenylanthracene derivative or the like as a guest material. In addition, styrylarylene derivatives such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9,10-bis. It can also be obtained from an anthracene derivative such as (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). Further, a polymer such as poly (9,9-dioctylfluorene) may be used.

More preferable specific examples are shown in Table 1.

The green luminescence is coumarin-based pigments such as coumarin 30 and coumarin 6, and bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It is obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. Further, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) _{2 Cl).} It can also be obtained from. Further, a polymer such as poly (p-phenylene vinylene) may be used.

More preferable specific examples are shown in Table 2.

Lubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-juloridyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) , Bis [2- (2-thienyl) pyridinato] Acetylacetonatolydium (abbreviation: Ir (thp) 2 (acac)), Bis (2-phenylquinolinato) Acetylacetonatoiridium (abbreviation: Ir (pq) (acac) )) Etc. can be obtained by using as a guest material. It can also be obtained from metal complexes such as bis (8-quinoquinolinolato) zinc (abbreviation: Znq2) and bis [2-cinnamoyle-8-quinolinolato] zinc (abbreviation: Znsq2). Further, a polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may be used.

More preferable specific examples are shown in Table 3.

Further, as the material used for the anode of the organic EL element used in the present invention, a metal having a large work function (4 eV or more), an alloy, an electrically conductive compound or a mixture thereof is preferably used as an electrode material. Specific examples of such an electrode material include metals such as Au and conductive materials such as _{CuI, ITO, SNO 2, and ZNO.} In order to form this anode, these electrode materials can be formed into a thin film by a method such as a thin film deposition method or a sputtering method. When the light emitted from the light emitting layer is taken out from the anode, it is desirable that the anode has a property that the transmittance of the anode with respect to the light emitted is larger than 10%. The sheet resistance of the anode ^{is preferably several hundred Ω / cm 2} or less. Further, the film thickness of the anode is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm, depending on the material.

Further, as the material used for the cathode of the organic EL element used in the present invention, a metal having a small work function (4 eV or less), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, rare earth metal and the like. This cathode can be produced by forming a thin film of these electrode materials by a method such as thin film deposition or sputtering. Here, when the light emitted from the light emitting layer is taken out from the cathode, the transmittance of the cathode with respect to the light emitted is preferably larger than 10%. The sheet resistance of the cathode ^{is preferably several hundred Ω / cm 2} or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

Regarding the method for producing the organic EL device used in the present invention, the anode, the light emitting layer, the hole injection layer if necessary, and the electron injection layer if necessary are formed by the above materials and methods, and finally the cathode is formed. It should be formed. Further, the organic EL element can be manufactured from the cathode to the anode in the reverse order of the above.

This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports an organic EL element, and its translucency is preferably such that the light transmittance in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more. It is preferable to use a smoother substrate.

These substrates are not particularly limited as long as they have mechanical and thermal strength and are transparent, but for example, a glass plate, a synthetic resin plate, or the like is preferably used. Examples of the glass plate include plates formed of soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz and the like. Examples of the synthetic resin plate include a plate such as a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, and a polysulfon resin.

As a method for forming each layer of the organic EL element used in the present invention, a dry film forming method such as vacuum vapor deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet. Wet film formation methods such as the method, a method of depositing a light emitter on a donor film, and Japanese Patent Publication No. 2002-534782 and S.A. T. Lee, et al. , Proceedings of SID '02, p. The LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet printing, and the like can also be applied.

The organic layer is particularly preferably a molecular deposition film. Here, the molecular deposition film is a thin film deposited and formed from a material compound in a gas phase state, or a film solidified and formed from a material compound in a solution state or a liquid phase state, and is usually this molecular deposition film. Can be classified from the thin film (molecular cumulative film) formed by the LB method by the difference in aggregate structure, higher-order structure, and the functional difference caused by the difference. Further, as disclosed in Japanese Patent Application Laid-Open No. 57-57181, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. Can also form an organic layer. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output and the efficiency deteriorates. On the contrary, if the film thickness is too thin, the pinhole Etc., and it becomes difficult to obtain sufficient emission brightness even if an electric field is applied. Therefore, the film thickness of each layer is preferably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.

Further, in order to improve the stability of the organic EL element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be coated or sealed with a resin or the like. In particular, when coating or sealing the entire element, a photocurable resin that is cured by light is preferably used.

The current applied to the organic EL element used in the present invention is usually direct current, but pulse current or alternating current may be used. The current value and voltage value are not particularly limited as long as they do not destroy the element, but considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electric energy as possible.

The organic EL element used in the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, as a method of extracting light from the organic EL element of the present invention, it can be applied not only to a method of bottom emission in which light is extracted from the anode side but also to a method of top emission in which light is extracted from the cathode side. These methods and techniques are described in Junji Kido, "All about Organic EL", Nihon Jitsugyo Publishing Co., Ltd. (published in 2003).

The main method of the full colorization method of the organic EL element used in the present invention is the color filter method. In the color filter method, an organic EL element that emits white light is used to extract light of the three primary colors through a color filter. In addition to these three primary colors, some white light is extracted as it is and used for light emission. , It is also possible to increase the luminous efficiency of the entire element.

Further, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which a light emitting layer is sandwiched between an anode and a cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode are transmitted. It is a technology that positively utilizes the multiple interference effect and controls the emission wavelength extracted from the element by appropriately selecting the optical characteristics such as the rate and the thickness of the organic layer sandwiched between them. .. This also makes it possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, refer to J.M. AM-LCD Digital Papers by Yamada et al., OD-2, p. 77-80 (2002).

An RGB color filter layer is produced by arranging it juxtaposed on a glass substrate or the like as described above, and an ITO electrode layer and a light emitting layer (backlight) produced by using the organic EL element are placed on the color filter layer. As a result, color display becomes possible, and a color display device can be obtained. At that time, it is possible to realize a color display device having a high contrast ratio by controlling the current flow at the time of light emission by the TFT.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

Further, a method for measuring the average primary particle size of the pigment, a method for identifying the azo pigment, a method for measuring the weight average molecular weight (Mw) of the resin, a method for measuring the acid value of the resin and the photopolymerizable compound, and a method for measuring the acid value of the photopolymerizable compound, and urethane for the photopolymerizable compound. The calculation method of the radix is as follows.

(Average primary particle size of pigment)
The average primary particle size of the pigment was measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment primary particles. Next, for 100 or more pigment particles, the volume (mass) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.

(Method for identifying azo pigments)
The azo pigment of the present invention is identified by using the MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonix, the molecular ion peak of the mass spectrum obtained, and the mass number obtained by calculation. It was identified with the agreement of.

(Quantity average molecular weight (Mn) and weight average molecular weight (Mw) of resin)
The quantity average molecular weight (Mn) and the weight average molecular weight (Mw) of the resin are GPC (Tosoh, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh), and THF is used as a developing solvent. It is a polystyrene-equivalent quantity average molecular weight (Mn) and weight average molecular weight (Mw) measured using.

(Acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1.0 part of the resin solution, stir to dissolve uniformly, and use a 0.1 mol / L KOH aqueous solution as a titrator to use an automatic titrator (“COM-555””. The acid value of the resin solution was measured by titration using (manufactured by Hiranuma Sangyo Co., Ltd.). Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Number of urethane groups of photopolymerizable monomer)
The number of urethane groups in the photopolymerizable monomer is a measure of the number of urethane bonds contained in the molecule, and was calculated below.
<Number of urethane bonds in one molecule obtained by the reaction of polyfunctional isocyanate> x <Ratio of polyfunctional acrylate generated by reaction in total photopolymerizable monomer> / <Average of photopolymerizable monomers Molecular weight>

(Number of double bond groups of photopolymerizable monomer)
The number of double bond groups of the photopolymerizable monomer is a measure of the number of double bonds contained in the molecule, and was calculated by the following formula.
<Average number of double bonds in one molecule> / <Average molecular weight of photopolymerizable monomer>
In the case of a mixture, the number of double bonds in one molecule of each component is multiplied by the mass ratio to the total photopolymerizable monomer, and the number of double bonds in all components is taken as the average number of double bonds in one molecule.

Subsequently, a method for producing an organic EL element, a resin-type dispersant solution, a binder resin solution, an azo pigment, other pigments, a colorant dispersion, and a photosensitive coloring composition used in Examples and Comparative Examples will be described.

<Manufacturing example of organic EL element>
A specific example of manufacturing an organic EL element used as a white light source is shown below. In the production examples of organic EL devices, all mixing ratios indicate mass ratios unless otherwise specified. The vapor deposition (vacuum vapor deposition) was ^{carried out in a vacuum of 10 -6} Torr (1.33 × 10 ^-4 Pa) under the conditions of no temperature control such as substrate heating and cooling. Further, in the evaluation of the light emission characteristics of the element, the characteristics of the organic EL element having an electrode area of 2 mm × 2 mm were measured.

(Manufacturing of organic EL element 1 (EL-1))
The washed glass plate with ITO electrode was treated with oxygen plasma for about 1 minute, and then 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited. A hole injection layer having a film thickness of 150 nm was obtained. On the hole injection layer, the compound (R-2) and the compound (R-3) in Table 3 are further co-deposited at a composition ratio of 100: 2 to form a first light emitting layer having a film thickness of 10 nm. bottom. Further, the compound (B-1) and the compound (B-4) in Table 1 were co-deposited at a composition ratio of 100: 3 to form a second light emitting layer having a film thickness of 20 nm. On the light emitting layer, α-NPD was further deposited at 5 nm and the compound (G-3) in Table 2 was deposited at 20 nm to form a third light emitting layer. Further, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form an electron-injected layer having a film thickness of 35 nm, on which lithium fluoride is first deposited by 1 nm and then aluminum is deposited by 200 nm to form an electrode. , An organic EL element was obtained.

Further, in order to protect the organic EL element from the surrounding environment, the organic EL element was hermetically sealed in a dry glove box filled with pure nitrogen. This element obtained white emission with a emission brightness of 950 (cd / m ² ), a maximum emission brightness of 55,000 (cd / m ² ), and a luminous efficiency of 3.9 (lm / W) at a DC voltage of 5 V. FIG. 1 shows the emission spectrum of the obtained organic EL element (EL-1).

The organic EL element peak wavelength lambda ₁ light emission intensity becomes maximum in each scope and wavelength 560nm~620nm of 430nm~485nm the (EL-1), and lambda _2, the emission intensity at the wavelength lambda ₁ I ₁ and the wavelength lambda ₂ The ratio of emission intensity I ₂ (I ₂ / I ₁ ) in Table 4 is shown in Table 4.

<Manufacturing method of resin type dispersant solution>
(Preparation of resin type dispersant solution C-1)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol is added to 10 parts. Time reacted. It was confirmed by solid content measurement that 95% had reacted. Add 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and react at 120 ° C. for 7 hours. rice field. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 77 mgKOH / g and a number average molecular weight of 8500. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution C-1 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution C-2)
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol is added to 10 parts. Time reacted. It was confirmed by solid content measurement that 95% had reacted. Add 36 parts of trimellitic acid anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and react at 120 ° C. for 7 hours. rice field. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain a polyester dispersant having an acid value of 109 mgKOH / g and a number average molecular weight of 8500. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution C-2 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution C-3)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and t-butyl were cooled. 16.0 parts of acrylate, 10.0 parts of hydroxymethyl methacrylate and 2.0 parts of ethyl acrylate were charged, and 0.10 part of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added. It reacted for 10 hours. It was confirmed by solid content measurement that the polymerization proceeded by 95%, and the reaction was terminated to obtain a polyester dispersant having an acid value of 43 mgKOH / g and a number average molecular weight of 15,000. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution C-3 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution C-4)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, 41.8 parts of methoxypropyl acetate was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C. and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70 ° C., and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and t-butyl were cooled. 16.0 parts of acrylate, 10.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate were charged, and 2,2'-azobisisobutyronitrile 0.10 part and methoxypropyl. 60.0 parts of acetate was added and reacted for 10 hours. It was confirmed by solid content measurement that the polymerization proceeded by 95%, and the reaction was terminated to obtain a polyester dispersant having an acid value of 47 mgKOH / g and a number average molecular weight of 15,000. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement to obtain a resin-type dispersant solution C-4 having an aromatic carboxyl group.

<Manufacturing method of binder resin solution>
(Preparation of acrylic resin solution 1)
196 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.) 20.7 A mixture of parts 2,2'-azobisisobutyronitrile and 1.1 parts was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol methyl is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Acrylic resin solution 1 was prepared by adding ether acetate. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
Put 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, and heat to 120 ° C. while injecting nitrogen gas into the vessel. At temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst required for the reaction of the precursor at this stage is 2.5 parts from the dropping tube. The polymerization reaction was carried out by dropping over time.
Next, the inside of the flask was replaced with air, and 29 parts of acrylic acid and 0.3 parts of trisdimethylaminomethylphenol and 0.3 parts of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the temperature was 120 ° C. for 5 hours. The reaction was carried out to obtain a resin solution having a weight average molecular weight (Mw) of about 10,500. Since the added acrylic acid is ester-bonded to the epoxy group terminal of the glycidyl methacrylate constituent unit, no carboxyl group is generated in the resin structure.
Further, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of the two carboxyl groups generated by cleavage of the carboxylic acid anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
Propylene glycol methyl ether acetate was added so that the non-volatile content was 20% by mass to obtain an acrylic resin solution 2. The weight average molecular weight (Mw) was 11,500 and the acid value was 103 mgKOH / g.

<Manufacturing method of azo pigment [A]>
(Base compound)
The base compounds ([B-1] to [B-5]) used this time are shown in Table 5.

(Manufacturing of coupler compound [C-1])

After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran, and 1 part of N, N-dimethylformamide, 221 parts of thionyl chloride is added, and the mixture is stirred at room temperature for 1 hour to prepare a carboxylic acid chloride solution. Obtained. Separately, a solution in which 1000 parts of N-methylpyrrolidone and 48 parts of 1,3-phenylenediamine were mixed was prepared, and a carboxylic acid chloride solution was added dropwise to this solution over 30 minutes. At this time, the dropping was performed while keeping the temperature of the reaction solution at 10 ° C. or lower. After completion of the dropping, the mixture was stirred at room temperature for 2 hours, and then the precipitated reaction product was collected by filtration to obtain the desired product. Further, the mixture was washed with 1000 parts of methanol and dried under reduced pressure to obtain 196 parts (yield 98.5%) of the coupler compound [C-1].

(Manufacturing of Coupler Compounds [C-2] to [C-17])
Instead of 48 parts of 1,3-phenylenediamine used in the production of the coupler compound [C-1], the diamines and parts by mass shown in Table 6 were changed, but the production of the coupler compound [C-1] was carried out. The same operation was carried out to produce the coupler compounds [C-2] to [C-17].

（アゾ顔料１の製造）

(Manufacturing of azo pigment 1)

After adding 169 parts of the base compound [B-1] to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added, and the mixture was cooled to -2 to 0 ° C. After adding 208 parts of a 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5 ° C. to prepare a diazonium solution. Separately, a coupler solution consisting of 167 parts of the coupler compound [C-1], 316 parts of a 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously added dropwise to 1000 parts of an acetate buffer solution having a pH of 5.4 in 10 minutes. After completion of the dropping, the mixture was stirred at room temperature for 30 minutes, further stirred while maintaining at 80 ° C., the precipitated reaction product was collected by filtration, washed with boiling water, and dried to add 337 parts of azo pigment 1 (yield:: 98.1%) obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 1.

（アゾ顔料２の製造）
アゾ顔料１の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−２］１８１部を使用した以外は、アゾ顔料１の製造と同様の操作を行い、アゾ顔料２を３４０部（収率：９５．６％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料２であることを同定した。 Azo pigment 1

(Manufacturing of azo pigment 2)
The same operation as in the production of the azo pigment 1 was performed except that 181 parts of the base compound [B-2] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 1. 2 was obtained in 340 parts (yield: 95.6%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 2.

（アゾ顔料３の製造）
アゾ顔料１の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−３］１２８部を使用した以外は、アゾ顔料１の製造と同様の操作を行い、アゾ顔料３を２９６部（収率：９７．９％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料３であることを同定した。 Azo pigment 2

(Manufacturing of azo pigment 3)
The same operation as in the production of the azo pigment 1 was performed except that 128 parts of the base compound [B-3] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 1. 3 was obtained in 296 parts (yield: 97.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 3.

（アゾ顔料４の製造）
アゾ顔料１の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−４］１８７部を使用した以外は、アゾ顔料１の製造と同様の操作を行い、アゾ顔料４を３５７部（収率：９８．９％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料４であることを同定した。 Azo pigment 3

(Manufacturing of azo pigment 4)
The same operation as in the production of the azo pigment 1 was performed except that 187 parts of the base compound [B-4] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 1. 4 was obtained in 357 parts (yield: 98.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 4.

（アゾ顔料５の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−３］１７２部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料５を３５２部（収率：９７．６％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料５であることを同定した。 Azo pigment 4

(Manufacturing of azo pigment 5)
The same operation as in the production of the azo pigment 2 was performed except that 172 parts of the coupler compound [C-3] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 352 parts (yield: 97.6%) of 5 was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 5.

（アゾ顔料６の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−４］１８３部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料６を３５３部（収率：９５．０％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料６であることを同定した。 Azo pigment 5

(Manufacturing of azo pigment 6)
The same operation as in the production of the azo pigment 2 was performed except that 183 parts of the coupler compound [C-4] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 6 was obtained in 353 parts (yield: 95.0%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 6.

（アゾ顔料７の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−５］１９７部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料７を３７９部（収率：９８．４％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料７であることを同定した。 Azo pigment 6

(Manufacturing of azo pigment 7)
The same operation as in the production of the azo pigment 2 was performed except that 197 parts of the coupler compound [C-5] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 7 was obtained in 379 parts (yield: 98.4%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 7.

（アゾ顔料８の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−６］１９０部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料８を３６８部（収率：９７．３％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料８であることを同定した。 Azo pigment 7

(Manufacturing of azo pigment 8)
The same operation as in the production of the azo pigment 2 was performed except that 190 parts of the coupler compound [C-6] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 8 was obtained in 368 parts (yield: 97.3%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 8.

Azo pigment 8

(Manufacturing of azo pigment 9)
The same operation as in the production of the azo pigment 2 was performed except that 189 parts of the coupler compound [C-7] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 373 parts (yield: 98.8%) of 9 was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 9.

（アゾ顔料１０の製造）
アゾ顔料１の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−２］２１９部を使用した以外は、アゾ顔料１の製造と同様の操作を行い、アゾ顔料１０を３９０部（収率：９８．７％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１０であることを同定した。 Azo pigment 9

(Manufacturing of azo pigment 10)
The same operation as in the production of the azo pigment 1 was performed except that 219 parts of the coupler compound [C-2] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 1. 10 was obtained in 390 parts (yield: 98.7%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 10.

（アゾ顔料１１の製造）
アゾ顔料１０の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−２］１８１部を使用した以外は、アゾ顔料１０の製造と同様の操作を行い、アゾ顔料１１を３９７部（収率：９７．４％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１１であることを同定した。 Azo pigment 10

(Manufacturing of azo pigment 11)
The same operation as in the production of the azo pigment 10 was performed except that 181 parts of the base compound [B-2] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 11 was obtained in 397 parts (yield: 97.4%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 11.

（アゾ顔料１２の製造）
アゾ顔料１０の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−３］１２８部を使用した以外は、アゾ顔料１０の製造と同様の操作を行い、アゾ顔料１２を３３７部（収率：９５．２％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１２であることを同定した。 Azo pigment 11

(Manufacturing of azo pigment 12)
The same operation as in the production of the azo pigment 10 was performed except that 128 parts of the base compound [B-3] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 12 was obtained in 337 parts (yield: 95.2%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 12.

（アゾ顔料１３の製造）
アゾ顔料１０の製造で使用したベース化合物［Ｂ−１］１６９部の代わりに、ベース化合物［Ｂ−５］１９０部を使用した以外は、アゾ顔料１０の製造と同様の操作を行い、アゾ顔料１３を４０５部（収率：９７．４％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１３であることを同定した。 Azo pigment 12

(Manufacturing of azo pigment 13)
The same operation as in the production of the azo pigment 10 was performed except that 190 parts of the base compound [B-5] was used instead of 169 parts of the base compound [B-1] used in the production of the azo pigment 10. 13 was obtained in 405 parts (yield: 97.4%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 13.

（アゾ顔料１４の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−８］１９５部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１４を３７５部（収率：９７．７％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１４であることを同定した。 Azo pigment 13

(Manufacturing of azo pigment 14)
The same operation as in the production of the azo pigment 2 was performed except that 195 parts of the coupler compound [C-8] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 14 was obtained in 375 parts (yield: 97.7%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 14.

（アゾ顔料１５の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−９］２６３部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１５を４３７部（収率：９６．９％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１５であることを同定した。 Azo pigment 14

(Manufacturing of azo pigment 15)
The same operation as in the production of the azo pigment 2 was performed except that 263 parts of the coupler compound [C-9] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 437 parts (yield: 96.9%) of 15 was obtained. As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 15.

（アゾ顔料１６の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１０］２０１部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１６を３８２部（収率：９８．１％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１６であることを同定した。 Azo pigment 15

(Manufacturing of azo pigment 16)
The same operation as in the production of the azo pigment 2 was performed except that 201 parts of the coupler compound [C-10] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 16 was obtained in 382 parts (yield: 98.1%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 16.

（アゾ顔料１７の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１１］２０７部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１７を３８３部（収率：９６．９％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１７であることを同定した。 Azo pigment 16

(Manufacturing of azo pigment 17)
The same operation as in the production of the azo pigment 2 was performed except that 207 parts of the coupler compound [C-11] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 17 was obtained in 383 parts (yield: 96.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 17.

（アゾ顔料１８の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１２］２０６部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１８を３８３部（収率：９７．３％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１８であることを同定した。 Azo pigment 17

(Manufacturing of azo pigment 18)
The same operation as in the production of the azo pigment 2 was performed except that 206 parts of the coupler compound [C-12] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 18 was obtained in 383 parts (yield: 97.3%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 18.

（アゾ顔料１９の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１５］２１２部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料１９を３９５部（収率：９８．７％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料１９であることを同定した。 Azo pigment 18

(Manufacturing of azo pigment 19)
The same operation as in the production of the azo pigment 2 was performed except that 212 parts of the coupler compound [C-15] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 19 was obtained in 395 parts (yield: 98.7%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 19.

（アゾ顔料２０の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１６］２１１部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料２０を３９０部（収率：９７．７％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料２０であることを同定した。 Azo pigment 19

(Manufacturing of azo pigment 20)
The same operation as in the production of the azo pigment 2 was performed except that 211 parts of the coupler compound [C-16] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 20 was obtained in 390 parts (yield: 97.7%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 20.

（アゾ顔料２１の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１７］２３７部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料２１を４０９部（収率：９６．０％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料２１であることを同定した。 Azo pigment 20

(Manufacturing of azo pigment 21)
The same operation as in the production of the azo pigment 2 was performed except that 237 parts of the coupler compound [C-17] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 21 was obtained in 409 parts (yield: 96.0%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 21.

（アゾ顔料２２の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１３］２２９部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料２２を４００部（収率：９５．８％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料２２であることを同定した。 Azo pigment 21

(Manufacturing of azo pigment 22)
The same operation as in the production of the azo pigment 2 was performed except that 229 parts of the coupler compound [C-13] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 22 was obtained in 400 parts (yield: 95.8%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 22.

（アゾ顔料２３の製造）
アゾ顔料２の製造で使用したカップラー化合物［Ｃ−１］１６７部の代わりに、カップラー化合物［Ｃ−１４］２４１部を使用した以外は、アゾ顔料２の製造と同様の操作を行い、アゾ顔料２３を４２３部（収率：９８．４％）得た。ＴＯＦ−ＭＳによる質量分析および元素分析の結果、アゾ顔料２３であることを同定した。 Azo pigment 22

(Manufacturing of azo pigment 23)
The same operation as in the production of the azo pigment 2 was performed except that 241 parts of the coupler compound [C-14] was used instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 2. 23 was obtained in 423 parts (yield: 98.4%). As a result of mass spectrometry and elemental analysis by TOF-MS, it was identified as the azo pigment 23.

（アゾ顔料２４の製造）
特開２０１４−１６０１６０号公報を参考にして下記のアゾ顔料２４を合成した。 Azo pigment 23

(Manufacturing of azo pigment 24)
The following azo pigment 24 was synthesized with reference to JP-A-2014-160160.

Azo pigment 24

(Manufacturing of PR-1) Miniaturization of azo pigment 80 parts of azo pigment 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. , Salt milling processed. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 78 parts of PR-1 were obtained.

(Manufacturing of PR-2) Miniaturization of azo pigment In the production of PR-1, the same as azo pigment 1 except that the azo pigment 1 and the dye derivative 1 shown below are changed to 90/10 instead of the azo pigment 1. And obtained PR-2.

(Production of PR-3 to 38) Miniaturization of azo pigment In the production of PR-1, the same as azo pigment 1 except that the azo pigment shown in Table 7 or an azo pigment and a derivative were changed instead of the azo pigment 1. Then, PR-3 to 38 were obtained.

誘導体２：下記化学式（１１）で表されるナフトール系色素誘導体

誘導体３：下記化学式（１２）で表されるキノフタロン系色素誘導体

誘導体４：下記化学式（１３）で表されるアゾ系色素誘導体

The structures of the derivatives in Table 7 are shown below.
Derivative 1: Naphthol-based dye derivative represented by the following chemical formula (10)

Derivative 2: Naphthol-based dye derivative represented by the following chemical formula (11)

Derivative 3: A quinophthalone-based dye derivative represented by the following chemical formula (12).

Derivative 4: Azo-based dye derivative represented by the following chemical formula (13)

(Manufacturing of PR-39) Miniaturization of PR177 Commercially available C.I. I. Pigment Red 177 (PR177) (Synic's "Cinilex Red SR3C") 100 parts, sodium chloride 1200 parts, and diethylene glycol 120 parts are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. And salt milling processing was performed. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 copies of PR-39 were obtained. The average primary particle size was 37 nm.

(Manufacturing of PR-40) Miniaturization of PR254 C.I. I. Pigment Red 177 (PR177) (“Cynic Red SR3C” manufactured by Cynic), C.I. I. Pigment Red 254 (“Irgazine Red D3656 HD” manufactured by BASF) was used in the same manner as in the production of PR-39 to obtain PR-40. The average primary particle size was 33 nm.

(Manufacturing of PY-1) Miniaturization of PY139 C.I. I. 100 parts of Pigment Yellow 139 (PY139) (BASF's "Pario Toll Yellow D1819"), 700 parts of sodium chloride, and 180 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. bottom. This mixture was put into 2000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, dried at 80 ° C. for 24 hours, and 95 parts of PY. I got -1. The average primary particle size was 43 nm.
(Production of PY-2) Miniaturization of quinophthalone compound (b) Compound (1) was obtained according to the synthesis method described in JP-A-2008-81566.

To 300 parts of methyl benzoate, 100 parts of compound (1), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. By TOF-MS, the formation of the quinophthalone compound (b) and the disappearance of the raw material compound (1) were confirmed. Further, after cooling to room temperature, the reaction mixture was added to 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of quinophthalone compound (b). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

Subsequently, 100 parts of the obtained quinophthalone compound (b), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water, stirred for 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 98 parts of PY-2 were obtained. The average primary particle size was 31.1 nm.

(Manufacturing of PY-3) Miniaturization of quinophthalone compound (a) Compound (2) was obtained according to the synthesis method described in JP-A-2008-81566.

To 300 parts of methyl benzoate, 100 parts of compound (2), 70 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 143 parts of benzoic acid were added, heated to 180 ° C., and reacted for 4 hours. By TOF-MS, the formation of the quinophthalone compound (a) and the disappearance of the raw material compound (2) were confirmed. Further, after cooling to room temperature, the reaction mixture was added to 3130 parts of acetone and stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 120 parts of the quinophthalone compound (a). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

Next, 100 parts of the quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product was put into 3 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. , 98 parts of PY-3 were obtained. The average primary particle size was 31.3 nm.

(Production of PY-4) Miniaturization of quinophthalone compound (c) To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride and 154 parts of benzoic acid were added to 180 parts. The mixture was heated to ° C. and stirred for 4 hours. Further, after cooling to room temperature, the reaction mixture was added to 5440 parts of acetone, and the mixture was stirred at room temperature for 1 hour. The product was filtered off, washed with methanol and dried to obtain 116 parts of the quinophthalone compound (c). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

Subsequently, 100 parts of the obtained quinophthalone compound (c), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water, stirred for 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. 97 parts of PY-4 were obtained. The average primary particle size was 34.1 nm.

(Manufacturing of PY-5) Miniaturization of PY185 C.I. used in the manufacture of PY-1. I. Pigment Yellow 139, C.I. I. Pigment Yellow 185 (PY185) (“Pariotor Yellow D1155” manufactured by BASF) was used, but the same procedure as in the production of PY-1 was carried out to obtain a yellow colorant (PY-5). The average primary particle size was 40.2 nm.

(Manufacturing of PG-1) Miniaturization of PG7 C. I. Add 200 parts of Pigment Green 7 (PG7) (Toyo Color Co., Ltd. "Rionol Green YS-07"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 120 ° C. Kneaded for 4 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, 490 parts of a green colorant (PG-1) was obtained. The average primary particle size was 55.3 nm.

(Manufacturing of PB-1) Miniaturization of PB15: 6 C.I. I. Pigment Blue 15: 6 (PB15: 6) (Toyo Color Co., Ltd. "Rionol Blue ES") 100 parts, crushed salt 800 parts, and diethylene glycol 100 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). It was kneaded at 70 ° C. for 12 hours. This mixture was put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, dried at 80 ° C. for 24 hours, and 98 parts of blue color. A colorant (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Manufacturing of PV-1) Miniaturization of PV23 C.I. I. Pigment Violet 23 (PV23) (Clariant "Fast Violet RL") 120 parts, crushed salt 1600 parts, and diethylene glycol 100 parts were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. .. This mixture was put into 5000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, dried at 80 ° C. for 24 hours, and 118 parts of purple. A colorant (PV-1) was obtained. The average primary particle size was 26.4 nm.

<Manufacturing method of colorant dispersion>
(Colorant Dispersion (DR-1))
The following mixture is stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 5 hours, and then the pore diameter is 5. A colorant dispersion (DR-1) was prepared by filtering with a 0 μm filter.

Red colorant (PR-2): 12.0 parts Resin type dispersant solution (C-1): 1.0 parts Acrylic resin solution 1: 35.0 parts Solvent: 52.0 parts Propylene glycol monomethyl ether acetate (PGMAC) )

(Colorant dispersion (DR-2 to 58, DY-1 to 5, DG-1, DB-1, DV-1))
Colorant dispersions (DR-2 to 58), (DY-1 to 5) in the same manner as the colorant dispersion (DR-1), except that the mixture was changed to a mixture having the composition (part by mass) shown in Table 8. , (DG-1), (DB-1), and (DV-1) were prepared.

誘導体６：下記化学式（１５）で表されるジケトピロロピロール系色素誘導体

Ｍｅはメチル基を表す。
誘導体７：下記化学式（１６）で表されるキノフタロン系色素誘導体

ＳＰ５５０００：ルーブリゾール社製「ＳＯＬＳＰＥＲＳＥ−５５０００」（固形分５０％））
ＢＹＫ２０００：ビックケミー社製「Ｄｉｓｐｅｒｂｙｋ−２０００」（固形分４０％）
ＢＹＫ６９１９：ビックケミー社製「ＢＹＫ−ＬＰＮ６９１９」（固形分６０％）
ＥＦＫＡ４３００：ＢＡＳＦ社製「ＥＦＫＡ４３００」（固形分８０％）
The abbreviations in Table 8 are shown below.

Derivative 5: Anthraquinone-based dye derivative represented by the following chemical formula (14)

Derivative 6: Diketopyrrolopyrrole dye derivative represented by the following chemical formula (15)

Me represents a methyl group.
Derivative 7: A quinophthalone-based dye derivative represented by the following chemical formula (16).

SP55000: "SOLSPERSE-55000" manufactured by Lubrizol (solid content 50%))
BYK2000: "Disperbyk-2000" manufactured by Big Chemie (solid content 40%)
BYK6919: "BYK-LPN6919" manufactured by Big Chemie (solid content 60%)
EFKA4300: "EFKA4300" manufactured by BASF (solid content 80%)

<Manufacturing of photopolymerizable compound C1>
Hexa / pentamixed acrylate of dipentaerythritol, 582 g, hexamethylene diisocyanate 36 g, and N, N-dimethylbenzylamine 0.5 g are charged in a 1 L volume four-necked flask and reacted at a temperature of 50 to 70 ° C. for 8 hours. , IR analysis confirmed the disappearance of isocyanate absorption.
24 g of mercaptopropionic acid and 0.6 g of 4-methoxyphenol were charged therein and reacted at a temperature of 50 to 60 ° C. for 6 hours to obtain a product containing a polyfunctional acrylate having a urethane bond and a carboxyl group.
The acid value of this photopolymerizable compound C1 was 28 mgKOH / g, and the content of the carboxyl group-containing polyfunctional monomer was 40% in terms of area by gel permeation chromatography. The number of urethane groups of the photopolymerizable compound C1 was 0.99 × 10 ^-3 mol / g, and the number of double bond groups was 8.08 × 10 ^-3 mol / g.

<Adjustment of Monomer A>
10 parts of "KAYARAD DPCA-60" manufactured by Nippon Kayaku Co., Ltd., 10 parts of "Aronix M-402" manufactured by Toagosei Co., Ltd., 20 parts of photopolymerizable compound C1 and 60 parts of methoxypropyl acetate are uniformly mixed and photopolymerizable. Monomer A was obtained as a metric.

<Adjustment of monomer B>
20 parts of "Aronix M-402" manufactured by Toagosei Co., Ltd., 10 parts of "Aronix M-309" manufactured by Toagosei Co., Ltd., 10 parts of "Aronix M-310" manufactured by Toagosei Co., Ltd., and 60 parts of propylene glycol methyl ether acetate are uniformly mixed. Then, monomer B was obtained as a photopolymerizable monomer.

<Adjustment of leveling agent A>
1 part of "BYK-330" manufactured by Big Chemie, 1 part of "MegaFuck F-551" manufactured by DIC Corporation, 1 part of "Emargen 103" manufactured by Kao Corporation, and 100 parts of propylene glycol monomethyl ether acetate are uniformly mixed and leveled. Agent A was obtained.

<Preparation of red coloring composition for organic EL display device>
[Example 1]
(Red Coloring Composition (RR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a red colored composition (RR-1).

Colorant Dispersion 1 (DR-1): 31.5 parts Colorant Dispersion 2 (DY-1): 13.5 parts Acrylic resin solution 2: 36.0 parts Monomer A: 10.5 parts Photopolymerization initiator (BASF "Irgacure OXE-02"): 1.2 parts Leveling agent A: 1.5 parts Solvent (Propylene glycol monomethyl ether acetate): 5.8 parts

[Examples 2-97, Comparative Examples 1-7]
(Coloring Compositions (RR-2 to 104)
Hereinafter, the types shown in Table 9 and the blending amount (part by mass) were stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a red colored composition (RR-2 to 104).

The abbreviations in Table 9 are shown below.

<Photopolymerization initiator>
OXE02: BASF's "Irgacure OXE-02"
IRG369: IGM Resins B.I. V. "Omnirad 369" manufactured by the company
OXE01: BASF's "Irgacure OXE-01"
Oxime 1: Oxime ester-based initiator represented by the chemical formula (8a-4) Oxime 2: Oxime ester-based initiator represented by the chemical formula (8b-2) Oxime 3: Oxime represented by the chemical formula (9-1) Oxime-based initiator Oxime 4: Oxime-based initiator represented by the chemical formula (9-2)

<Sensitizer>
DETX: "KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.

Thiol: Pentaerythritol terakis (3-mercaptopropionate)
Epoxy: "EHPE-3150" manufactured by Daicel
Silane coupling agent: "KBM-403" manufactured by Shinetsu Silicone Co., Ltd.
Antioxidant: "IRGANOX1010" manufactured by BASF
Solvent: Propylene glycol monomethyl ether acetate

[Evaluation of photosensitive red coloring composition]
The color characteristics, film thickness, and patterning characteristics of the photosensitive red coloring compositions obtained in Examples and Comparative Examples were evaluated by the following methods. Table 10 shows the evaluation results.

<Formation of filter segment>
A black matrix is patterned on a glass substrate, and the coloring composition shown in Table 9 is used on the substrate with a spin coater. In an organic EL element (EL-1) as a light source, x (EL-1) is 0. It was applied to a film thickness of 670 to form a film of a coloring composition. The film was irradiated with ultraviolet rays of ^{150 mJ / cm 2} using an ultrahigh pressure mercury lamp via a photomask. Then, with an alkaline developer consisting of 0.15% by mass of sodium carbonate, 0.05% by mass of sodium hydrogen carbonate, 0.1% by mass of an anionic surfactant ("Perirex NBL" manufactured by Kao Co., Ltd.) and 99.7% by mass of water. After spray developing to remove the unexposed portion, the substrate was washed with ion-exchanged water and heated at 230 ° C. for 20 minutes to form the red filter segment shown in Table 10.

<Color characteristics / film thickness evaluation>
The color characteristics (x, y, Y) of the red filter segment when the obtained red filter segment is irradiated with light using the organic EL element 1 (EL-1) as a light source are measured by a microscopic photometer (Olympus Optical Co., Ltd.). It was measured using "OSP-SP100") manufactured by Japan.
The film thickness was measured using a surface shape measuring instrument DEKTAK150 (manufactured by ULVAC, Inc.).
<Evaluation of patterning characteristics>
[Linearity evaluation]
The pattern on the 100 μm photomask portion of the filter segment or the black matrix formed by the above method was observed and evaluated using an optical microscope. The evaluation ranks are as follows.
◯: Good linearity △: Partially poor linearity ×: Poor linearity

本発明の一般式（１）および（２）で表されるアゾ顔料を用いた感光性着色組成物は、フィルタセグメントが高い明度Ｙを示した。またパターニング特性も良好であった。

In the photosensitive coloring composition using the azo pigments represented by the general formulas (1) and (2) of the present invention, the filter segment showed a high brightness Y. The patterning characteristics were also good.

<Manufacturing color filters for organic EL display devices>
(Photosensitive green coloring composition (RG-1))
The mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a photosensitive green coloring composition (RG-1).

Colorant dispersion (DG-1): 45.1 parts Colorant dispersion (DY-5): 21.6 parts Acrylic resin solution 2: 4.3 parts "Aronix M402" manufactured by Toagosei Co., Ltd. (photopolymerizable simple substance) Quantitative body): 4.2 parts IGM Resins B. V. "Omnirad 907" (photopolymerization initiator): 1.2 parts "EAB-F" (sensitizer) manufactured by Hodogaya Chemical Co., Ltd .: 0.4 parts Propylene glycol monomethyl ether acetate: 23.2 parts

(Photosensitive blue coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a photosensitive blue coloring composition (RB-1).

Colorant dispersion (DB-1): 24.6 parts Colorant dispersion (DV-1): 12.9 parts Acrylic resin solution 2: 23.0 parts "Aronix M402" manufactured by Toagosei Co., Ltd. (photopolymerizable simple substance) Quantitative body): 2.1 parts IGM Resins B. V. "Omnirad 907" (photopolymerization initiator): 0.6 parts Hodogaya Chemical Co., Ltd. "EAB-F" (sensitizer): 0.2 parts Propylene glycol monomethyl ether acetate: 36.6 parts

[Example 98]
(Color filter (CF-1))
Using the photosensitive red coloring composition (RR-15), a red filter segment formed by the same method as the formation of the filter segment was formed. Similarly, the photosensitive green coloring composition (RG-1) is used to form a green filter segment with a film thickness of y = 0.700 when the organic EL element 1 (EL-1) is used, and then the photosensitive green filter segment is formed. A blue filter segment was formed so that y = 0.080 using the blue coloring composition (RB-1) to obtain a color filter (CF-1).

[Examples 99 to 102, Comparative Example 8]
(Color filter (CF-2 to 6))
In the same manner as in Example 98 (color filter (CF-1)), except that the photosensitive red coloring composition shown in Table 11 was used instead of the photosensitive red coloring composition (RR-15), ( Color filters (CF-2 to 6) were obtained.

<Evaluation of color filter>
The color characteristics of the color filter when the color filters produced in Examples and Comparative Examples are irradiated with light using the organic EL element 1 (EL-1) are measured by a microscopic photophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). Was measured using. Chromaticity points (x, y) in the CIE color system of each color filter segment, three primary colors of the standard method defined by the NTSC ratio (American National Television System Committee (NTSC), red (0.67, 0.33), Table 11 shows the brightness (Y value) of green (0.21, 0.71), blue (0.14, 0.08) and the area surrounded by blue (0.14, 0.08).

A color filter (CF-1 to 5) containing a red filter segment formed by a red coloring composition containing an azo pigment represented by the general formula (1) or (2) maintains a high brightness of a white display. However, it was confirmed that the color reproducibility was as wide as 99% of NTSC.

Claims (7)

Organic EL display containing a colorant containing an azo pigment [A] represented by the following general formulas (1) and / or (2), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator [B]. Red coloring composition for equipment.

General formula (1)

[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. .. R ₂ and R ₃ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
Independently, X _{1 to} X ₄ are a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group and a sulfo group. , Represents a halogen atom. ]

General formula (2)

[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and an aryloxy group which may have a substituent. .. R ₅ and R ₆ independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X _{5 to} X ₁₂ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, and a halogen atom. A represents a direct bond or a divalent linking group. As the divalent linking group, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO _2- , -COO-, -CONH-, and -SO ₂ NH- are used. show. ] The colorant is further C.I. I. The red coloring composition for an organic EL display device according to claim 1, wherein the pigment yellow 139 and at least one pigment selected from the group consisting of a quinophthalone compound represented by the following general formula (3) are contained. ..

General formula (3)

[In the general formula (3), Z _{1 to} Z ₁₃ independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, and a substituent. It may have an aryl group, -SO ₃ H, -COOH, and monovalent to trivalent metal salt thereof acidic groups, alkylammonium salt, an optionally substituted phthalimidomethyl group, or a substituent The sulfamoyl group which may have is shown.
Adjacent groups of Z _{1 to} Z ₄ and / or Z _{10 to} Z ₁₃ may together form an aromatic ring that may have a substituent. ] The red coloring composition for an organic EL display device according to claim 1 or 2, wherein the photopolymerization initiator [B] contains an oxime ester-based photopolymerization initiator [B1]. In a color filter for an organic EL display device including at least one red filter segment, at least one green filter segment, and at least one blue filter segment, at least one red filter segment is the organic EL according to any one of claims 1 to 3. A color filter for an organic EL display device formed of a red coloring composition for a display device. Has at least the peak wavelength lambda _1, each emission intensity and scope of a wavelength 430nm~485nm and wavelength 560nm~620nm is maximized, the lambda _2, the emission intensity in the emission intensity I ₁ and the wavelength lambda ₂ at a wavelength lambda ₁ I _{When a} white organic EL light source having spectral characteristics in which the ratio to ₂ (I 2 / I ₁ ) is 0.4 or more and 0.9 or less is used, the chromaticity coordinates of the colored film in the XYZ color system are obtained. When (xR, yR), (xG, yG), (xB, yB), the areas of the triangle surrounded by these three points are red (0.67, 0.33) and green (0.21,). 0.71) The color filter for an organic EL display device according to claim 4, wherein the color filter is 75% or more of the area surrounded by blue (0.14, 0.08). An organic EL display device comprising the color filter for the organic EL display device according to claim 4 or 5 and a white organic EL light source. _{The white organic EL light source has peak wavelengths λ 1} and λ ₂ that maximize the emission intensity in at least the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, respectively, and has emission intensity I ₁ and wavelength at _{wavelength λ 1.} The organic EL display device according to claim 6, wherein the organic EL display device according to claim 6 has an emission spectrum in which the ratio (I ₂ / I ₁ ) to the emission intensity I _{2 at} λ _{2 is 0.4 or more and 0.9 or less.}

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