JP2017116767A - Photosensitive colored composition, color filter and organic el display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored composition which requires no process of uniformly controlling lightness of a color filter or varying a light source output in an organic EL display device using a white light-emitting organic EL element as a light source, and which allows formation of an organic EL display device having good heat resistance without inducing changes in chromaticity of white, relating to heat resistance in a post process of a color filter.SOLUTION: The photosensitive colored composition is to be used for a color filter substrate having at least a red pixel, a green pixel and a blue pixel. The photosensitive colored composition (a) comprises a colorant (A), a binder resin (B), a photopolymerizable compound (C) and a photopolymerization initiator (D). The colorant (A) comprises a green dye and a red dye, in which the green dye is included by 20 to 60 wt.% and the red dye is included by 10 to 70 wt.% in the colorant. The colorant (A) is included by 1 to 18 wt.% in a solid content of the composition.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a photosensitive coloring composition for a transmittance adjusting layer, a color filter, which is preferably used in a color display device using a white light-emitting organic EL (electroluminescence) element (hereinafter sometimes referred to as “organic EL element”). And a color display device. White means a broad concept including pseudo white.

  Examples of color display devices using color filters include (i) a backlight as a light source, a liquid crystal as an optical shutter, and a combination of color filters having color adjustment functions (color conversion function, color separation function, color correction function, etc.) And (ii) a synthetic white organic EL light source, and an organic EL display device comprising a combination of color filters having a color adjustment function (color conversion function, color separation function, color correction function, etc.).

  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. Synthetic white light is obtained by mixing or layering.

  Since the organic EL display device can directly turn on / off the light source of the pixel by a TFT (thin film transistor) or the like, it is possible to perform black display by turning off the light emission of the designated pixel. Therefore, the deflecting plate used in the liquid crystal display device is not required in the light emitting device, and it is not necessary to control the liquid crystal body. For this reason, the amount of transmitted light in the display device increases, and energy consumption can be greatly reduced by turning off the light emitting device in 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 in which the problems in the liquid crystal display device are solved, for example, a product such as “XEL-1” manufactured by SONY is already on the market. (For example, see Patent Document 1)

  However, a light emitting device using such an organic EL element has a light emission spectrum different from that of a conventionally used light source. 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. In addition, the emission spectrum of the light source using the organic EL element has a broad peak as compared with the conventional light source, and therefore, even after passing the peak around 460 nm, the conventional light source reaches about 500 nm. The spectrum is higher. For these reasons, currently used color filters cannot be used as they are in display devices using light sources using organic EL elements. For this reason, it is necessary to select and develop a color filter material that can be used for a light source using an organic EL element and has an optimum hue and transmittance characteristics.

  On the other hand, in recent years, a four-color color filter substrate has been proposed in a liquid crystal display device in order to achieve high transmittance of the color filter. For example, Patent Document 2 proposes a four-color filter having cyan pixels in addition to red, green, and blue pixels. The spectral transmittance at 400 nm is 45% or more, and the spectral transmittance at 550 nm is 50% or more. It is described.

  Patent Document 3 proposes a four-color filter substrate in which white pixels are added as fourth pixels in addition to red, green, and blue pixels, and since it contains an appropriate amount of colorant, the transmittance is not lowered. It is described that the additive color mixture chromaticity of red, green and blue pixels is matched with the chromaticity of white pixels to improve the white balance.

  However, since the color characteristics of white are defined by the chromaticity and brightness of each color, conventionally, it has been necessary to change the chromaticity of the three colors in order to adjust the color temperature of white. As a result, in order to set white as the target color temperature, the target of chromaticity of each color cannot be achieved. Alternatively, it has been studied to adjust white to a target color temperature without changing the chromaticity of the three colors by independently adjusting the brightness of each color filter segment in the coloring composition (for example, Patent Documents 4 and 4). 5) is not sufficient.

  In particular, in a backlight light source using an organic EL element, it is known that the emission spectrum changes when the output of the light source is suppressed in order to adjust the luminance. This may cause changes in white chromaticity and color temperature, and may change the display color of the entire color display device and impair visibility.

  In Patent Document 2, the fourth color cyan pixel takes into account the white balance due to the additive color mixture of the four colors, but the white balance is improved because the transmittance of the cyan pixel is considerably low. The transmittance is not improved. Furthermore, since the formation of the protective film in the subsequent process goes through a process of 220 ° C., the heat resistance of the cyan pixel is required, and there is a concern that the luminance is lowered.

  In Patent Document 3, the white balance is improved in the liquid crystal display device, which is not described in the processability evaluation after the formation of the fourth pixel, and the blue pigment is essential in the examples, so that the heat resistance is patented. There is concern for the same reason as in Document 2.

Japanese Patent Laid-Open No. 2005-10091 JP 2010-282211 A JP 2012-150457 A JP 2004-279617 A JP 2004-309537 A

  The photosensitive coloring composition of the present invention is an organic EL display device using a white light-emitting organic EL element as a light source, and adjusts the brightness of the color filter evenly, without changing the light source output, and in the process after the color filter. As for heat resistance, without changing the chromaticity of white, a photosensitive coloring composition for a transmittance adjusting layer capable of forming an organic EL display device having good heat resistance, a color filter formed using the composition, An object of the present invention is to provide an organic EL display device.

  As a result of intensive studies to solve the above problems, the present inventors have found that a photosensitive coloring composition containing a colorant containing a specific amount of a green dye and a red dye has excellent heat resistance and a transmittance adjusting layer. For this purpose, the present inventors have found that an organic EL display device excellent in white chromaticity and color temperature is made possible, and have made the present invention based on this finding.

That is, the present invention is a photosensitive coloring composition for a color filter substrate having at least a red pixel, a green pixel and a blue pixel,
A photosensitive coloring composition (a) used for a pixel other than the red pixel, the green pixel and the blue pixel, or used for a colored layer formed on or below the red pixel, the green pixel and the blue pixel. ,
The photosensitive coloring composition (a) contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), and the colorant (A) is green. A pigment and a red pigment,
The green pigment is contained in an amount of 20 to 60% by weight based on the whole colorant (A),
The red pigment is contained in an amount of 10 to 70% by weight based on the whole colorant (A),
A coloring agent (A) is related with the photosensitive coloring composition characterized by being contained 1 to 18weight% with respect to solid content of the said photosensitive coloring composition (a).

  Moreover, this invention relates to the said photosensitive coloring composition in which a coloring agent (A) contains further at least 1 sort (s) of pigment | dye chosen from the group which consists of a blue pigment | dye, a yellow pigment | dye, and a purple pigment | dye.

  Moreover, this invention relates to the said photosensitive coloring composition whose blue pigment | dye is 40 weight% or less with respect to the whole coloring agent (A).

  Further, the present invention provides the photosensitive coloring composition, wherein the green pigment contains at least one selected from the group consisting of a phthalocyanine pigment and an aluminum phthalocyanine pigment represented by the following general formula (1): Related to things.

General formula (1)

[In General Formula (1), X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyclo which may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl group that may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ]

  Further, the present invention provides the photosensitive coloring composition, wherein the red dye contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment, an anthraquinone pigment, an azo pigment, and a perylene pigment. Related to things.

  The present invention also relates to the photosensitive coloring composition, wherein the yellow pigment contains at least one selected from the group consisting of isoindoline pigments and quinophthalone pigments.

  Moreover, this invention relates to the said photosensitive coloring composition which is an object for the transmittance | permeability adjustment layers.

  The present invention also relates to a color filter having a red pixel, a green pixel, a blue pixel, and a transmittance adjusting layer formed from the photosensitive coloring composition.

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

  The photosensitive coloring composition of the present invention is excellent in heat resistance even after the filter segment is formed, there is little change in white balance, the brightness of the color filter is adjusted uniformly, the light source output is not changed, and the visibility is also good. An organic EL display device can be formed.

It is an example of the emission spectrum of a white organic EL light source (EL-1).

Hereinafter, the present invention will be described in detail.
In the present application, when “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” is particularly described, Unless otherwise indicated, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. It shall represent.
Further, “CI” in this specification means a color index (CI).

<< Photosensitive coloring composition >>
The photosensitive coloring composition (a) of the present invention is a photosensitive coloring composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), Further, the colorant (A) contains a green colorant and a red colorant, the green colorant is 20 to 60% by weight with respect to the whole colorant (A), and the red colorant is 10 to 70 with respect to the whole colorant (A). The content of the colorant (A) in the solid content of the photosensitive coloring composition (a) is 1 to 18% by weight.

<Colorant (A)>
The colorant (A) can be used by mixing an organic or inorganic pigment, or a pigment that is a dye. The organic pigment is preferably a pigment having high color developability and high heat resistance.

The colorant (A) of the present invention must contain a green pigment and a red pigment,
Furthermore, since at least one colorant selected from the group consisting of a blue colorant, a yellow colorant, and a purple colorant is included, the change in white chromaticity when used as a transmittance adjusting layer is small, and heat resistance is improved. Is preferred.
The range of the content of the colorant (A) contained in the photosensitive coloring composition (a) of the present invention is 1 to 18% by weight, preferably 1 to 15% by weight, more preferably 1 to 10% by weight. This is preferable because good white balance can be obtained while maintaining the brightness. If the content is too high, the lightness of the photosensitive coloring composition (a) of the present invention is lowered, and if the content is too low, a good white balance cannot be obtained.

[Green pigment]
As the green colorant in the present invention, a pigment or a dye can be used. Among them, it is preferable to contain a green pigment,
As the green pigment, for example, a phthalocyanine pigment or an aluminum phthalocyanine pigment represented by the following formula (1) is preferably used.

General formula (1)

[In General Formula (1), X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyclo which may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl group that may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ]

Among the phthalocyanine pigments, C.I. I. Pigment Green 7, 10, 36, 37, 58, 59 and an aluminum phthalocyanine pigment represented by the general formula (1) can be used.
Among these, C.I. I. Pigment Green 7, 36, 58, 59 and at least one green pigment selected from the group consisting of green pigments such as aluminum phthalocyanine pigments represented by the general formula (1), used as a transmittance adjusting layer Is preferable because the change in chromaticity of white is small and the heat resistance is high.
The range of the content of the green pigment contained in the photosensitive coloring composition of the present invention with respect to the colorant (A) is 20 to 60% by weight, preferably 20 to 50% by weight, more preferably 20 to 40% by weight. It is. Within the above range, the content of the blue pigment can be reduced, and the heat resistance can be improved while maintaining the white balance.

[Red dye]
As the red pigment in the present invention, a pigment or a dye can be used.
Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 166, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, Red pigments such as 242, 246, 254, 255, 264, 269, and 272 can be used.
Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Among these, the red pigment is preferably a diketopyrrolopyrrole pigment, an anthraquinone pigment, an azo pigment, or a perylene pigment. Furthermore, C.I. I. Pigment Red254, C.I. I. Pigment Red177, C.I. I. Pigment Red 269, or C.I. I. Pigment Red 179 is preferable because the change in white chromaticity is small when used as a transmittance adjusting layer. Moreover, the range of content with respect to the coloring agent (A) of a red pigment | dye contains 10 to 70 weight%, Preferably it is 10 to 60 weight%, More preferably, it is 10 to 50 weight%. If the red pigment is contained outside the above range, the lightness of the transmittance adjusting layer is lowered and the white balance is lowered.

[Blue dye]
As the blue colorant in the present invention, a pigment or a dye can be used.
Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17: 1, 24, 24: 1, 25, 26, And blue pigments such as 56, 60, 61, 62, 63, 64, and 75.
In addition, a basic dye or a salt-forming compound of an acidic dye exhibiting a blue color can be used. When the dye is used, a triarylmethane dye is preferable.

  Among these, C.I. I. Pigment Blue 15: 6 or C.I. I. Pigment Blue 15: 3 is preferable because the change in white chromaticity is small when used as a transmittance adjusting layer. The content of the blue pigment with respect to the colorant (A) is 40% by weight or less, preferably 35% by weight or less, more preferably 30% by weight or less. When the content of the blue pigment with respect to the colorant (A) exceeds 40% by weight, the heat resistance of the blue pigment is low, which causes a decrease in white balance after the heat test.

[Yellow pigment]
A pigment or dye can be used as the yellow pigment in the present invention.
Examples of yellow pigments include 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, 81,182,185,187,188,193,194,198,199,213,214,218,219,220, or it can be used yellow pigment 221, and the like.
Also, yellow dyes such as quinoline, azo, disazo, and methine can be used.
Among these, isoindoline pigments and quinophthalone pigments are preferable. Among these, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, C.I. I. In the case of including Pigment Yellow 185, the change in white chromaticity is small when used for the transmittance adjusting layer.

[Purple dye]
As the purple pigment, a pigment or a dye can be used.
Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. Purple pigments can be used.
Further, a basic dye having a purple color or a salt-forming compound of an acid dye can be used. When a dye is used, a xanthene dye is preferable.
Among these, C.I. I. In the case of including Pigment Violet 23, the change in white chromaticity is small when used as a transmittance adjusting layer.

[Orange dye]
Further, as the colorant (A), in addition to the above dyes, other dyes such as orange dyes can be used.
Examples of orange pigments that are orange dyes include C.I. I. Orange pigments such as Pigment Orange 36, 38, 43, 64, 71, or 73 can be used.
In addition, orange dyes such as quinoline, azo, disazo, and methine dyes can also be used.

  Among these colorants, C.I. I. Pigment Green 7, 36, 58, 59 or an aluminum phthalocyanine pigment represented by the following general formula (1) is essential, and C.I. I. Pigment Red254, 177, 269 or 179, C.I. I. Pigment Blue 15: 6 or 15: 3, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 139, or C.I. I. Pigment Yellow 185, C.I. I. By combining an organic pigment of at least one color selected from the group of Pigment Violet 23, the transmittance does not become a biased value at a specific wavelength, and the white chromaticity greatly deviates when used as a transmittance adjusting layer. It is preferable because there is nothing.

General formula (1)

[In General Formula (1), X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyclo which may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl group that may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ]

(Miniaturization of pigment)
The pigment used in the present invention can be used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. It can be performed.
By making these pigments finer, they can be suitably used as a photosensitive coloring composition for adjusting transmittance.

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

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  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 cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from both the processing efficiency and the production efficiency.

  The water-soluble organic solvent functions to wet 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 to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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 weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, 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 weight with respect to 100 parts by weight of the pigment.

<Binder resin (B)>
The binder resin (B) disperses, dyes, or penetrates the pigment, and includes a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. 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. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin (B) 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 (B) 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 disperse the colorant preferably. . 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 (B) is used as a photosensitive coloring composition for a color filter, a carboxyl group that acts as a colorant adsorption group and an alkali-soluble group during development, a fat that acts as an affinity group for the colorant carrier and solvent The balance between the group and the aromatic group is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin (B) is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high and good. Since color characteristics can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin (B) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, 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, etc. Is mentioned. Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be 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 and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a 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 a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers 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 or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) that may be added to the photosensitive coloring composition of the present invention includes a monomer or oligomer that is cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by 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 ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds (C) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

The blending amount of the photopolymerizable compound (C) is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable.
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

<Photopolymerization initiator (D)>
As photopolymerization initiator (D), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, Is a benzoin compound such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6- Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole A imidazole compound; a titanocene compound, or the like.
These photopolymerization initiators (D) can be used singly or as a mixture of two or more at any ratio as required.

  Among these, it is more preferable that an oxime ester type compound is included as a photoinitiator (D). An oxime ester compound is preferable because it has a very high sensitivity and can form a lightness adjusting layer in a short exposure.

  The content of the photopolymerization initiator (D) is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant (A), and is 3 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

<Sensitizer>
Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition, and 5 to 50 from the viewpoint of photocurability and developability. More preferred are parts by weight.

<Solvent>
The photosensitive coloring composition of the present invention can contain a solvent. Thereby, the coloring agent is sufficiently dispersed and permeated in the photosensitive coloring composition, and is applied on a substrate such as a glass substrate so as to have a dry film thickness of 0.5 to 5.0 μm to form a colored film. Can be made easier.

Examples of the solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2 -Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-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, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethyl Formamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, 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 monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopro 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 Len glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl 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, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, from the viewpoint of storage stability of the colored composition of the present invention, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, glycol acetates such as ethylene glycol monoethyl ether acetate, benzyl alcohol, etc. It is preferable to use ketones such as aromatic alcohols and cyclohexanone.

  Since the content of the solvent can adjust the colored composition to an appropriate viscosity and can form a colored film having a desired uniform film thickness, the amount of the solvent is 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant (A). It is preferable to use in.

<Multifunctional thiol>
The photosensitive coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the weight (100% by weight) of the total solid content of the photosensitive coloring composition. If the content of the polyfunctional thiol is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and if it exceeds 30% by weight, the sensitivity is too high and the resolution is lowered.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, yellowing due to oxidation during the heating process can be prevented by including an antioxidant.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

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

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.

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

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding 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 end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane 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 thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the photosensitive coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, 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 derivatives bicyclic amidine compounds and salts thereof (eg imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl) -4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example tri Phenylphosphine ), Guanamine compounds (for example, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-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 do. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, 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-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition of the present invention comprises a kneader, a two-roll mill, a colorant (A) in a colorant carrier such as a binder resin (B) and / or a solvent, preferably together with a dispersion aid. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, at least three colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  The photosensitive coloring composition (resist material) for color filters can be prepared as a solvent developing type or alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, the photopolymerizable compound (C), and the photopolymerization initiator (D), and, if necessary, a solvent, other dispersion aids, and It can be adjusted by mixing additives and the like. The photopolymerization initiator (D) may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing re-aggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has spectral characteristics and viscosity stability. Will be better.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving the dispersibility of the added colorant. It is. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40 parts by weight or less, more preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

<Resin type dispersant>
The resin-type dispersant has a colorant affinity part that has the property of adsorbing to the added colorant, and a part that is compatible with the colorant carrier, and adsorbs to the added colorant to disperse in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants 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 polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles and the like are preferred.
The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight relative to the total amount of the pigment, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

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

<Removal of coarse particles>
The photosensitive coloring composition of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a coarse particle of 0.5 μm or more by means such as centrifugation, filtration with a sintered filter or a membrane filter. It is preferable to remove particles and mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter for organic EL display devices of the present invention will be described.
The color filter of the present invention comprises the photosensitive coloring composition for a transmittance adjusting layer of the present invention.

  The color filter includes a red pixel (red filter segment), a green pixel (green filter segment), and a blue pixel (blue filter segment), and further includes a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment. It may be provided.

  As an embodiment of the transmittance adjusting layer using the photosensitive coloring composition of the present invention, when used as a fourth color pixel, which is equivalent to a red pixel, a green pixel and a blue pixel, for example, transmittance adjustment Examples of the layer include a case where it is used for a colored layer formed on or below all or some of red pixels, green pixels, and blue pixels.

  When used for the color filter for the transmittance adjusting layer, it may be formed on each color filter segment, or after forming the color filter for the transmittance adjusting layer on the substrate before forming the filter segment, the filter segment is formed. May be. Alternatively, it may be formed on the back surface of the color filter substrate.

In the color filter for adjusting transmittance according to the present invention, the chromaticity (x, y) represented by CIE 1931 is preferably 0.250 ≦ x ≦ 0.350, 0.250 ≦ y ≦ 0.310, It is preferable that 0.265 ≦ x ≦ 0.310 and 0.260 ≦ y ≦ 0.305.
The chromaticity (x, y) of the fourth color pixel in the present invention is preferably 0.250 ≦ x ≦ 0.350, and more preferably 0.275 ≦ x ≦ 0.320. The chromaticity y of the fourth color pixel is preferably 0.250 ≦ y ≦ 0.310, and 0.260 ≦ y ≦ 0.
. More preferably, it is 305. By setting the chromaticity (x, y) of the pixel of the fourth color in the above range, it is easy to achieve both white balance and high transmittance of the color filter substrate of the present invention.

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

  Colored film formation by printing can be patterned simply by repeating printing and drying of a photosensitive coloring composition prepared as a printing ink, and as a color filter manufacturing method, it is low-cost and excellent in mass productivity. . Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When forming a colored film by a photolithography method, the photosensitive coloring composition prepared as the solvent developing type or alkali developing type coloring resist material is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the photosensitive coloring composition of the present invention can be used in any method. The electrodeposition method is a method for manufacturing a color filter by using a transparent conductive film formed on a substrate and forming a colored film on the transparent conductive film by electrodeposition of colloidal particles. . 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 this colored film is transferred to a desired substrate.

If the 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 increased. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but 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 luminance can be improved.
On the color filter of the present invention, an overcoat film or a transparent conductive film is formed as necessary.

<Organic EL display device>
The organic EL display device in the present invention is a photosensitive coloring composition for a color filter substrate having at least a red pixel, a green pixel and a blue pixel,
A photosensitive coloring composition (a) used for a pixel other than the red pixel, the green pixel and the blue pixel, or used for a colored layer formed on or below the red pixel, the green pixel and the blue pixel. And
The photosensitive coloring composition (a) contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). The colorant (A) is green A pigment and a red pigment,
The green pigment is contained in an amount of 20 to 60% by weight based on the whole colorant (A),
The red pigment is contained in an amount of 10 to 70% by weight based on the whole colorant (A),
The colorant (A) is contained in an amount of 1 to 18% by weight based on the solid content of the photosensitive coloring composition (a), and a color filter formed of the photosensitive coloring composition, which emits white light A display device having an organic EL element (hereinafter referred to as an organic EL element) as a light source is preferable.

(Organic EL element (white light-emitting organic EL element))
The organic EL device used in the present invention has peak wavelengths (λ1) and (λ2) at which the emission intensity becomes maximum in at least the wavelength range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm, and emits light at the wavelength λ1. The ratio of the intensity I1 to the emission intensity I2 at the wavelength λ2 (I2 / I1) preferably has an emission spectrum of 0.4 or more and 0.9 or less, and is 0.5 or more and 0.8 or less Is more preferable. Most preferably, it is 0.5 or more and 0.7 or less.
It is preferable that the emission intensity I2 ratio (I2 / I1) has an emission spectrum of 0.4 or more and 0.9 or less because high brightness and wide color reproducibility can be obtained.

Furthermore, it is preferable that the light emission intensity has a maximum value 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 the color display device including the color filter displays blue with good color reproducibility. More preferably, it is the range of 430 nm-475 nm.
By using the organic EL element satisfying these configurations and the color filter, a color display device having a wide color reproduction region and high brightness can be obtained.

  An organic EL element is comprised from the element which formed the organic layer of one layer or a multilayer between the anode and the cathode. Here, the single-layer organic EL element refers to an element composed of only a light emitting layer between an anode and a cathode, while the multilayer organic EL element refers to a hole or a hole 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 smooth recombination of holes and electrons in the light emitting layer It refers to a laminate of layers. Therefore, typical element configurations of the multilayer organic EL element include (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 include an anode / light emitting layer / hole blocking layer / electron injection layer / cathode, and (8) an element configuration laminated in a multilayer structure such as anode / light emitting layer / electron injection layer / cathode. However, the organic EL element used in the present invention is not limited to these.

  Moreover, each organic layer mentioned above may be formed by the layer structure of 2 or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device 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 There is a method of laminating a plurality of portions.

  First, materials that can be used for each of these layers are specifically exemplified. However, 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-based compound is effective, and copper phthalocyanine (abbreviation: CuPc), vanadyl phthalocyanine (abbreviation: VOPc), or the like can be used. There are also materials obtained by chemically doping conductive polymer compounds, such as polyethylenedioxythiophene (abbreviation: PEDOT) doped with polystyrene sulfonic acid (abbreviation: PSS), polyaniline (abbreviation: PANI), or the like. You can also. In addition, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoOx), vanadium oxide (abbreviation: VOx), nickel oxide (abbreviation: NiOx), and ultrathin films of inorganic insulators such as aluminum oxide (abbreviation: Al2O3) are also effective. It is. 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 (abbreviation) : TPD), 4,4′-bis [N- (1-naphthyl) -N-phenyl-amino] -biphenyl (abbreviation: α-NTPD), 4,4′-bis [N- (4- (N, Aromatic amine compounds such as (N-di-m-tolyl) amino) phenyl-N-phenylamino] biphenyl (abbreviation: DNTPD) can also be used. Further, a substance showing acceptability with respect to 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), or α-NPD to which acceptor MoOx is added may be used.

  As a material that can be used for the hole transport layer, an aromatic amine compound is preferable, and TDATA, MTDATA, TPD, α-NPD, DNTPD, and the like described for 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-quinolinolato) aluminum (abbreviation: Alq3), tris (4-methyl-8-quinolinolato) aluminum (abbreviation: Almq3), bis (10-hydroxybenzo). [H] -quinolinato) beryllium (abbreviation: BeBq2), bis (2-methyl-8-quinolinolato) (4-phenylphenolato) aluminum (abbreviation: BAlq), bis [2- (2-hydroxyphenyl) benzoxazola And metal complexes such as zinc (substantially: Zn (BOX) 2) and bis [2- (2-hydroxyphenyl) benzothiazolate] zinc (substantially: Zn (BTZ) 2). In addition to metal complexes, 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (abbreviation: PBD), 1,3-bis [5- Oxadiazole derivatives such as (p-tert-butylphenyl) -1,3,4-oxadiazol-2-yl] 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 Imidazole] (abbreviated Imidazole derivatives such as TPBI), bathophenanthroline (abbreviation: can be used phenanthroline derivatives such as BCP): BPhen), bathocuproine (abbreviation.

  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, TPBI, described above. Electron transport materials such as BPhen and BCP can be used. In addition, an ultra-thin film of an insulator such as an alkali metal halide such as LiF or CsF, an alkaline earth halide such as CaF2, or an alkali metal oxide such as Li2O is often used. In addition, alkali metal complexes such as lithium acetylacetonate (abbreviation: Li (acac)) and 8-quinolinolato-lithium (abbreviation: Liq) are also effective. Further, a substance exhibiting a donor property with respect to these electron injection materials may be added to the electron injection material, and alkali metals, alkaline earth metals, rare earth metals, and the like can be used as donors. Specifically, a material obtained by adding lithium as a donor to BCP or a material obtained by adding lithium as a donor to Alq3 can be used.

  Furthermore, a hole blocking material that can prevent holes from passing through the light emitting layer from reaching the electron injection layer and form a layer having excellent thin film formability is used for the hole blocking layer. Examples of such hole blocking materials include aluminum complex compounds such as bis (8-hydroxyquinolinato) (4-phenylphenolato) aluminum, and bis (2-methyl-8-hydroxyquinolina). -To) (4-phenylphenolato) gallium complex compounds such as gallium, nitrogen-containing condensed aromatic compounds such as 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (abbreviation: BCP) Can be mentioned.

  Although there is no restriction | limiting in particular as a light emitting layer which obtains white light emission, For example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined and light is emitted using tunnel injection (European Patent No. 0390551). Similarly, a white light-emitting element is an example of an element using tunnel injection. What is described (JP-A-3-230584), a light-emitting layer having a two-layer structure (JP-A-2-220390 and JP-A-2-216790), and a plurality of light-emitting layers A layered material composed of materials having different emission wavelengths (Japanese Patent Laid-Open No. 4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm), Further, a red phosphor is included (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, and the green light emitting layer is a red fluorescent dye. It has contained area, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.

  Further, as the light emitting material used in the present invention, a material known as a conventional light emitting material may be used. Examples of compounds suitably used for blue, green, orange to red light emission are shown below. However, the light emitting material is not limited to those specifically exemplified below.

  Blue light emission can be obtained by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivative, or the like as a guest material, for example. Further, styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi), 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). A polymer such as poly (9,9-dioctylfluorene) may also be used.

  Further preferred specific examples are shown in Table 1.

  Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenylpyridinato) acetyl. It can be obtained by using acetonatoiridium (abbreviation: Ir (ppy) (acac)) or the like as a guest material. Also from metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq3), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) 2Cl). Can be obtained. A polymer such as poly (p-phenylene vinylene) may also be used.

Further preferred specific examples are shown in Table 2.

  Light emission from orange to red is caused by rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2- Methyl-6- (9-julolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (abbreviation: BisDCM) Bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (abbreviation: Ir (pq) (acac) )) Etc. as a guest material. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). A polymer such as poly (2,5-dialkoxy-1,4-phenylenevinylene) may be used.

  Further preferred specific examples are shown in Table 3.

Furthermore, the material used for the anode of the organic EL device used in the present invention is preferably a material having a work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance. Specific examples of such an electrode substance include metals such as Au, and conductive materials such as CuI, ITO, SNO2, and ZNO. In order to form this anode, a thin film can be formed from these electrode materials by a method such as vapor deposition or sputtering. The anode desirably has such a characteristic that when light emitted from the light emitting layer is extracted from the anode, the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / cm ² or less. Further, although the film thickness of the anode depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

The material used for the cathode of the organic EL device used in the present invention is a material having a work function (4 eV or less) metal, alloy, electrically conductive compound and a mixture thereof as an electrode substance. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / silver alloy, aluminum / aluminum oxide, aluminum / lithium alloy, indium, and rare earth metals. This cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Here, when light emitted from the light-emitting layer is extracted from the cathode, the transmittance of the cathode for light emission is preferably greater than 10%. Further, the sheet resistance as 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, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. What is necessary is just to form. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

  This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.

  These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include plates made 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 plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone 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 deposition, electron beam beam irradiation, sputtering, plasma, ion plating, or spin coating, dipping, flow coating, inkjet A wet film-forming method such as a method, a method of vapor-depositing a light emitter on a donor film, JP-A-2002-534882, and S. T. T. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.

  The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Also, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, and then this is thinned by a spin coat method or the like. Also, an organic layer can be formed. 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, resulting in poor efficiency. Conversely, if the film thickness is too thin, the pinhole is used. Or the like, and even when an electric field is applied, it is difficult to obtain sufficient light emission luminance. Accordingly, the thickness of each layer is suitably 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 covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, 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 a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as they are within the range that does not destroy the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.

  The driving method of 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, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).

  The main method of the full color method of the organic EL element used in the present invention is a color filter method. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter. In addition to these three primary colors, a part of white light is extracted as it is and used for light emission. In addition, the luminous efficiency of the entire device can be increased.

  Furthermore, the organic EL element used in the present invention may adopt a microcavity structure. This is because the organic EL device has a structure in which the light emitting layer is sandwiched between the anode and the 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 This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).

  As described above, an RGB color filter layer is produced in parallel with a glass substrate, and a light emitting layer (backlight) produced using the ITO electrode layer and the organic EL element is placed on the color filter layer. As a result, color display is possible, and a color display device is obtained. At this time, a color display device having a high contrast ratio can be realized by controlling the current flow during 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 weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  Moreover, the measuring method of the weight average molecular weight (Mw) of resin is as follows.

(Weight average molecular weight of resin (Mw))
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

  Then, the manufacturing method of the organic EL element, the binder resin solution, the refined pigment, the pigment dispersion, and the red, green, and blue photosensitive coloring compositions used in Examples and Comparative Examples will be described.

<Method for producing organic EL element>
The production example of the organic EL element used as a white light source is specifically shown below. In the production examples of organic EL elements, all the mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 ⁻⁶ Torr and under conditions without temperature control such as substrate heating and cooling. In the evaluation of the light emission characteristics of the element, the characteristics of an organic EL element having an electrode area of 2 mm × 2 mm were measured.

(Manufacture of organic EL element (EL-1))
After the cleaned glass plate with the ITO electrode was treated with oxygen plasma for about 1 minute, 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum deposited, A hole injection layer having a thickness of 50 nm was obtained. On this hole injection layer, the compound (R-2) and the compound (R-3) shown in Table 4 are vacuum-deposited at a composition ratio of 100: 0.5 to form a first light emitting layer having a thickness of 20 nm. Further, the compound (B-3) and the compound (B-4) shown in Table 2 were co-evaporated at a composition ratio of 100: 2 to form a second light emitting layer having a thickness of 40 nm. On this light emitting layer, a tris (8-hydroxyquinoline) aluminum complex is vacuum-deposited to form a third light emitting layer having a film thickness of 30 nm. Further, α-NPD is 5 nm, and tris (8-hydroxyquinoline) aluminum complex is formed. Was vacuum-deposited to form an electron injection layer having a thickness of 20 nm, on which lithium fluoride was deposited to a thickness of 1 nm and aluminum was further deposited to a thickness of 300 nm to form an electrode to obtain an organic EL device.

Furthermore, in order to protect this organic EL element from the surrounding environment, it was hermetically sealed in a dry glow box filled with pure nitrogen. This device obtained white light emission with a direct current voltage of 5 V and an emission luminance of 1500 (cd / m ² ), a maximum emission luminance of 55000 (cd / m ² ), and an emission efficiency of 3.9 (lm / W). FIG. 1 shows an emission spectrum of the obtained organic EL element (EL-1).

  The peak wavelengths (λ1) and (λ2) at which the emission intensity is maximized in the range of 430 nm to 485 nm and the wavelength range of 560 nm to 620 nm of the organic EL element (EL-1), the emission intensity I1 at the wavelength λ1, and the emission wavelength at the wavelength λ2 Table 4 shows the ratio (I2 / I1) of the emission intensity I2.

<Method for producing binder resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. 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 Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add PGMAC to the previously synthesized resin solution so that the nonvolatile content is 20 wt% Thus, an acrylic resin solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20 wt% Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Production method of fine pigment>
(Green fine pigment (PG-1))
Phthalocyanine green pigment C.I. I. Pigment Green 7 (PG7) (“Rionol Green YS-07” manufactured by Toyocolor Co., Ltd.), 1500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. For 8 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. As a result, a green fine pigment (G1) was obtained. The average primary particle size was 55.5 nm.

(Green fine pigment (PG-2))
C. I. Pigment Green 7 is C.I. I. Pigment Green 36 (PG36) (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.) was used in the same manner as in the production of the green fine pigment (PG-1), and the green fine pigment (PG-2) was used. Obtained. The average primary particle size was 35.4 nm.

(Green fine pigment (PG-3))
C. I. Pigment Green 7 is replaced with phthalocyanine green pigment C.I. I. Except having changed to Pigment Green 58 (DIC Corporation "FASTOGEN GREEN A110"), it carried out similarly to manufacture of the green refined pigment (PG-1), and obtained the green refined pigment (PG-3). The average primary particle size was 51.3 nm.

(Green fine pigment (PG-4))
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following general formula (2).

General formula (2)

(Green refined pigment (PG-5))
In a reaction vessel, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the general formula (2) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following general formula (3).
100 parts of the obtained aluminum phthalocyanine pigment represented by the formula (54), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . The kneaded product is poured into 3000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for a whole day and night. A fine pigment (PG-5) was obtained. The average primary particle size was 31.2 nm.

General formula (3)

(Green fine pigment (PG-6))
In a reaction container, 100 parts of methanol and 100 parts of an aluminum phthalocyanine pigment represented by the general formula (2) and 43.2 parts of diphenylphosphinic acid were added to 1000 parts of methanol, heated to 40 ° C., and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and then dried to obtain 112 parts of an aluminum phthalocyanine pigment represented by the following general formula (4).
The resulting aluminum phthalocyanine pigment represented by the general formula (4) was subjected to a salt milling treatment similar to that of the green fine pigment 5 (PG-5) to obtain a green fine pigment (PG-6). The average primary particle size was 29.5 nm.

General formula (4)

(Red refined pigment (PR-1))
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) (“Irgafore Red B-CF” manufactured by BASF), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 6 ° C. The mixture was kneaded for a time and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red refined pigment (PR-1) were obtained. The average primary particle size was 33 nm.

(Red fine pigment (PR-2))
C. I. Pigment Red 254, C.I. I. Pigment Red 179 (PR179) (“Pariogen Maroon L-3920” manufactured by BASF) was used in the same manner as in the production of red fine pigment (PR-1), and red fine pigment (PR-2) 97 Got a part. The average primary particle size was 40.8 nm.

(Red fine pigment (PR-3))
C. I. Pigment Red 254, C.I. I. Pigment Red 177 (PR177) (“chromophthal red A2B” manufactured by BASF) was used in the same manner as in the production of red fine pigment (PR-1), and 97 parts of red fine pigment (PR-3) Got. The average primary particle size was 27.6 nm.

(Red fine pigment (PR-4))
C. I. Pigment Red 254, C.I. I. Except for changing to Pigment Red 269 (PR269) ("Toner Magenta F8B" manufactured by Clariant), it was carried out in the same manner as in the production of red fine pigment (PR-1), and 97 parts of red fine pigment (PR-4) was added. Obtained. The average primary particle size was 35 nm.

(Blue refined pigment (PB-1))
C. I. 100 parts of Pigment Blue 15: 6 (PB15: 6) (“Rionol Blue ES” manufactured by Toyocolor Co., Ltd.), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho), 70 The mixture was kneaded for 12 hours. The mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 98 parts of blue A refined pigment (PB-1) was obtained. The average primary particle size was 28.3 nm.

(Blue refined pigment (PB-2))
C. I. Pigment Blue 15: 6 (PB15: 6) was changed to C.I. I. Pigment Blue 15: 3 (PB15: 3) (“Lionol Blue FG-7351” manufactured by Toyocolor Co., Ltd.) was used in the same manner as in the production of the blue refined pigment (PB-1). -2) was obtained in an amount of 98. The average primary particle size was 30.3 nm.

(Yellow fine pigment (PY-1))
Isoindoline yellow pigment C.I. I. 100 parts of Pigment Yellow 139 ((PY139) (“Irgafore Yellow 2R-CF” manufactured by BASF)), 800 parts of ground salt and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. The mixture was kneaded for 4 hours, poured into 3000 parts of warm water, stirred for about 1 hour with a high-speed mixer while being heated to about 80 ° C., and then filtered and washed with water to remove salt and solvent, It dried at 80 degreeC for 24 hours, and obtained 96 parts of yellow refinement | purification pigment (PY-1).

(Yellow refined pigment (PY-2))
C. I. Pigment Yellow 139 is C.I. I. Pigment Yellow 185 (PY185) (“Pariogen Yellow D1155” manufactured by BASF) was used in the same manner as in the production of yellow refined pigment (PY-1) to obtain a yellow refined pigment (PY-2). . The average primary particle size was 40.2 nm.

(Yellow finer pigment (PY-3))
C. I. Pigment Yellow 139 was changed to CI Pigment Yellow 138 (PY138) ("Pariotol Yellow K0960-HD" manufactured by BASF Corporation) in the same manner as in the production of yellow refined pigment (PY-1). Pigmented pigment (PY-3) was obtained. The average primary particle size was 30.5 nm.

(Purple refined pigment (PV-1))
C. I. 120 parts of Pigment Violet 23 (PV23) (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. . The mixture was poured into 5000 parts of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 118 parts of purple A fine pigment (PV-1) was obtained. The average primary particle size was 26.4 nm.

<Method for producing pigment dispersion>
(Pigment dispersion (DG-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DR-1) was produced.

Green refined pigment (PG-1): 12.0 parts Resin type dispersant (“EFKA4300” manufactured by BASF): 1.0 part Acrylic resin solution 1: 35.0 parts Solvent (PGMAC): 52.0 parts

(Pigment dispersion (DG-2 to 6, DR-1 to 4, DB-1, 2, DY-1 to 3, DV-1))
The pigment dispersions (DG-2 to 6), (DR-1 to 4), (DR-1 to 4) are the same as the pigment dispersion (DG-1) except that the mixture has a composition (parts by weight) shown in Table 5. DB-1 and 2), (DY-1 to 3), and (DV-1) were prepared.

<Method for producing red, green, and blue photosensitive coloring composition>
Subsequently, the mixture shown in Table 6 was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain each color-sensitive colored composition (alkali developing resist materials RR, GR, BR). In Table 6, “Aronix M402” manufactured by Toagosei Co., Ltd. was used as the photopolymerizable compound, and “Irgacure OXE-02” (Ethanone, 1- [9-ethyl] manufactured by Ciba Japan Co., Ltd. was used as the photopolymerization initiator. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)) was used. Further, as the leveling agent solution, a solution obtained by diluting 2 parts of “BYK-330” (non-volatile content: 100% by weight) manufactured by Big Chemie with 98 parts of propylene glycol monomethyl ether acetate (PGMAC) was used.

[Example 1]
(Photosensitive coloring composition (RW-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered and mixed with a 1.0 μm filter to prepare a photosensitive coloring composition (RW-1).
Pigment dispersion DG-1 (PG7): 4.4 parts Pigment dispersion DR-1 (PR254): 2.3 parts Pigment dispersion DR-4 (PR269): 2.9 parts Acrylic resin solution 2: 23.8 Part photopolymerizable compound “Aronix M402” manufactured by Toagosei Co., Ltd .: 2.3 parts photopolymerization initiator “IRGACURE OXE-02” manufactured by BASF: 0.8 part leveling agent solution: 1.0 part “BYK” manufactured by BYK Chemie -330 "(non-volatile content 100% by weight)) 2 parts propylene glycol monomethyl ether acetate (PGMAc)
Solution solvent diluted with 98 parts (PGMAC): 62.5 parts

[Examples 2 to 24, Comparative Examples 1 to 8]
(Photosensitive coloring composition (RW-2 to 32)
Hereinafter, the photosensitive coloring composition (except for the color composition, the acrylic resin solution, the photopolymerizable compound, the photopolymerization initiator, the sensitizer, and the solvent shown in Table 7, except that the types and amounts (parts by weight) were changed). In the same manner as in RW-1), photosensitive colored compositions (RW-2 to 32) were produced. As a photopolymerizable compound in Table 7, “Aronix M402” manufactured by Toagosei Co., Ltd. was used, and as a photopolymerization initiator, “Irgacure OXE-02” (Etanone, 1- [9-ethyl] manufactured by Ciba Japan Co., Ltd. was used. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)) was used. Further, as the leveling agent solution, a solution obtained by diluting 2 parts of “BYK-330” (non-volatile content: 100% by weight) manufactured by Big Chemie with 98 parts of propylene glycol monomethyl ether acetate (PGMAC) was used.

(Evaluation of photosensitive coloring composition (RW-1 to 24))
[Example 25]
<Red, Green, Blue, and Color Filter (CF-1) Formation Using Photosensitive Coloring Composition of the Present Invention>
In the organic EL device (EL-1) as a light source by patterning a black matrix on a glass substrate and using the red coloring composition (RR) shown in Table 6 on the substrate with a spin coater, x in Table 8; Each film was applied to a film thickness such that the value of y was formed to form a red colored composition film. The film was irradiated with ultraviolet rays of 150 mJ / cm 2 using a super high pressure mercury lamp through a photomask. Next, an alkaline developer composed of 0.1% by weight of sodium carbonate 0.15% by weight sodium hydrogen carbonate 0.05% by weight anionic surfactant ("PERIREL NBL" manufactured by Kao Corporation) and 99.7% by weight of water After removing the unexposed portion by spray development, the substrate was washed with ion exchange water, and this substrate was heated at 230 ° C. for 20 minutes to form a red filter segment. Next, in the same manner, using the green photosensitive coloring composition (GG) shown in Table 6, the blue coloring composition (BB) shown in Table 6, and the photosensitive coloring composition (RW-1) shown in Table 7, A color filter (CF-1) having a red pixel, a green pixel, a blue pixel, and a fourth pixel was created.

[Examples 26 to 48, Comparative Example 9-16]
(Color filter (CF-2-32))
In the same manner as in Example 1 color filter (CF-1) except that the photosensitive coloring composition described in Table 9 was used instead of the photosensitive coloring composition (RW-1) for the fourth pixel, Color filters (CF-2 to 32) were obtained.

[Comparative Example 17]
<Creation of a color filter (CF-33) having no fourth pixel>
In the same manner as in Example 1, a color filter (CF-33) having no fourth pixel was obtained.

<Evaluation of color filter (CF-33)>
(Color characteristic evaluation)
The color characteristic (x, y, Y) when the color filter obtained in Comparative Example 17 was irradiated with light using the organic EL element 1 (EL-1) as a light source was measured with a microspectrophotometer (manufactured by Olympus Optical Co., Ltd.). “OSP-SP100”).

(Heat resistance evaluation)
The color filter (CF-33) obtained above was heated at 230 ° C. for 1 hour as a heat resistance test, and the chromaticity of each of the red, green and blue filter segments with the C light source ([L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the following formula.

ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )

  Table 8 shows the result of color characteristics before and after the heat resistance evaluation of the color filter having no fourth pixel, the heat resistance evaluation, and the chromaticity of the additive color mixture.

  As shown in Table 8, the color difference in the heat resistance test was small in the order of green> red> blue in each filter segment.

<Evaluation of color filters (CF-1 to 32)>
(Heat resistance evaluation)
The color filter (CF-1 to 32) obtained above was heated at 230 ° C. for 1 hour as a heat resistance test, the color characteristics (x, y) of the fourth pixel before and after the heat resistance test, the results of white balance, and the white balance Table 9 shows the results of the differences (|| Δx | before the heat test− | Δx | after the heat test |, || Δy | before the heat test− | Δy | after the heat test |).
The evaluation criteria for the difference in white balance are as follows. In the evaluation results, ◎ and ○ are good, Δ is a level that does not cause a problem in use, and × corresponds to a state where it cannot be used.

◎ ... White balance difference before and after heat test 0 to less than 0.005 ○ ... White balance difference before and after heat test 0.000 to less than 0.010 Δ ... White balance before and after heat test The difference of 0.010 or more and less than 0.015 ×... The white balance difference before and after the heat test is 0.015 or more.

Examples 25-31 and 39-48 are the results of the color filter having the fourth pixel not containing the blue pigment, and white before and after the durability test as compared to Examples 32-38 having the fourth pixel containing the blue pigment. The difference in balance did not change greatly and was good.
Further, when the blue pigment was 40% by weight or less in the total weight of the pigment, the difference in white balance did not change greatly, and it was at a level with no problem in use.

Furthermore, compared with Comparative Examples 10-16, the 4th pixel containing the green pigment of this invention did not change a white balance largely in the heat test of a color filter, and was a favorable result.

Claims (9)

A photosensitive coloring composition for a color filter substrate having at least a red pixel, a green pixel and a blue pixel,
A photosensitive coloring composition (a) used for a pixel other than the red pixel, the green pixel and the blue pixel, or used for a colored layer formed on or below the red pixel, the green pixel and the blue pixel. ,
The photosensitive coloring composition (a) contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), and the colorant (A) is green. A pigment and a red pigment,
The green pigment is contained in an amount of 20 to 60% by weight based on the whole colorant (A),
The red pigment is contained in an amount of 10 to 70% by weight based on the whole colorant (A),
1 to 18 weight% of coloring agents (A) are contained with respect to solid content of the said photosensitive coloring composition (a), The photosensitive coloring composition characterized by the above-mentioned. The photosensitive coloring composition according to claim 1, wherein the colorant (A) further comprises at least one dye selected from the group consisting of a blue dye, a yellow dye, and a purple dye. 3. The photosensitive coloring composition according to claim 2, wherein the blue pigment is 40% by weight or less based on the entire colorant (A). The photosensitive material according to claim 1, wherein the green dye contains at least one selected from the group consisting of a phthalocyanine pigment and an aluminum phthalocyanine pigment represented by the following general formula (1). Coloring composition.
General formula (1)
[In General Formula (1), X _{1 to} X ₄ are each independently an alkyl group which may have a substituent, an aryl group which may have a substituent, or a cyclo which may have a substituent. An alkyl group, a heterocyclic group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio group which may have a substituent, or The arylthio group which may have a substituent is represented.
Y _{1 to} Y ₄ each independently represent a halogen atom, a nitro group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group.
Z represents a hydroxyl group, a chlorine atom, —OP (═O) R ₁ R ₂ , or —O—SiR ₃ R ₄ R ₅ . Here, R _{1 to} R ₅ are each independently a hydrogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl group that may have a substituent. Or an aryloxy group which may have a substituent, and Rs may be bonded to each other to form a ring. m _{1 to} m ₄ and n _{1 to} n ₄ each independently represents an integer of 0 to 4, and m ₁ + n ₁ , m ₂ + n ₂ , m ₃ + n ₃ , m ₄ + n ₄ are each 0 to 4 may be the same or different. ] 5. The photosensitive material according to claim 1, wherein the red dye contains at least one selected from the group consisting of a diketopyrrolopyrrole pigment, an anthraquinone pigment, an azo pigment, and a perylene pigment. Coloring composition. The photosensitive coloring composition according to claim 2 or 3, wherein the yellow pigment contains at least one selected from the group consisting of isoindoline pigments and quinophthalone pigments. The photosensitive coloring composition according to claim 1, which is used for a transmittance adjusting layer. A color filter having a transmittance adjusting layer formed of a red pixel, a green pixel, a blue pixel, and the photosensitive coloring composition according to claim 1. An organic EL display device comprising the color filter according to claim 8 and a white organic EL light source.