JP2019138983A - Photosensitive colored composition for organic el display device, color filter and organic el display device - Google Patents

Abstract

Kind Code: A1 An object of the present invention is to provide an organic EL display device which has high sensitivity, linearity, wide pattern shape and shape margin, and excellent resolution, development resistance, and chemical resistance even when the pigment content is high or the film thickness is thick. An object of the present invention is to provide a photosensitive coloring composition, a color filter using the same, and an organic EL display device. [Means for Solving Problem] The above problem is achieved by combining a coloring agent (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an alkali-soluble resin (D), and a silane coupling agent (E). 42 to 60% by mass of a coloring agent (A), 15 to 35% by mass of a photopolymerizable compound (C), and 0.0% of a silane coupling agent (E) based on the total solid content in the photosensitive coloring composition. 1 to 10% by mass, and the photopolymerizable compound (C) has at least in the molecule at least one bond selected from the group consisting of a urethane bond and a bond derived from caprolactone modification. Solved by the coloring composition. [Selection drawing] Fig. 1

Description

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

  As a synthetic white light source of an organic EL display device, 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 overlapping. However, a light emitting device using such an organic EL element is currently used in a display device using a light source using an organic EL element because the light emission spectrum of a conventionally used light source is different from the emission spectrum. At present, the color filter cannot be used as it is. 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.

  In addition, an organic EL display device having such a light source is also required to have a high NTSC ratio, similar to a liquid crystal display device. In order to increase the NTSC ratio, it is necessary to increase the color purity of each filter segment.

  In order to increase the color purity of the filter segment, it is necessary to increase the pigment content in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the pigment content, problems such as sensitivity reduction, developability, and resolution deteriorate. In the method of increasing the film thickness, there is a problem that the exposure light does not reach the bottom of the film and the pattern shape becomes defective.

  In order to solve such problems, in Patent Documents 1 and 2, (1) provision of a reactive double bond of a resin, (2) selection or increase of a photopolymerization initiator and a sensitizer, and (3) selection of a monomer Alternatively, it has been proposed to increase the sensitivity of the photosensitive coloring composition by increasing the amount, but there is a limit to improving the sensitivity only by imparting a double bond of the resin or selecting a photopolymerization initiator, sensitizer and monomer. The required performance could not be met.

JP 2001-264530 A JP 2003-156842 A

  The present invention has high sensitivity, high linearity, pattern shape and shape margin, excellent resolution, development resistance, and chemical resistance, even if the pigment content is high or the film thickness is large. An object is to provide a coloring composition, a color filter using the same, and an organic EL display device.

  The present invention relates to the following <1> to <8> photosensitive coloring composition for organic EL display devices, <9> color filters, and <10> organic EL display devices.

<1> Organic EL display containing a colorant (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an alkali-soluble resin (D), and a silane coupling agent (E) It is the photosensitive coloring composition for apparatuses, Comprising: Colorant (A) 42-60 mass%, Photopolymerizable compound (C) 15-35 mass%, Silane coupling in the total solid in a photosensitive coloring composition The agent (E) is contained in an amount of 0.1 to 10% by mass, and the photopolymerizable compound (C) has at least one bond selected from the group consisting of a urethane bond and a bond derived from caprolactone modification in the molecule. A photosensitive coloring composition for an organic EL display device.

<2> The photosensitive coloring composition for organic EL display devices according to claim 1, wherein the silane coupling agent (E) has an unsaturated double bond.

<3> The photosensitive coloring composition for an organic EL display device according to claim 1, further comprising an antioxidant (F) and / or a polymerization inhibitor (G).

<4> The photosensitive coloring composition for organic EL display devices according to claim 3, wherein the antioxidant (F) contains a hindered phenol compound.

<5> The organic EL display according to any one of claims 1 to 4, wherein the colorant (A) contains a red pigment and a yellow pigment, and the red pigment contains a pigment represented by the following general formula (1). Photosensitive coloring composition for apparatus.
General formula (1)

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

<6> The colorant (A) is C.I. I. The photosensitive coloring composition for organic electroluminescent display devices of any one of Claims 1-5 containing Pigment Red 269.

<7> The photosensitive coloring composition for organic EL display devices according to any one of claims 1 to 6, wherein the photopolymerization initiator (B) contains a compound represented by the following general formula (2).
General formula (2)

[In General Formula (2), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, substituted or Unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl Represents a group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]

<8> The photosensitive coloring composition for organic EL display devices according to claim 7, wherein the compound represented by the general formula (2) is a compound represented by the following formula (3) or the following formula (4).
Formula (3)

Formula (4)

A color filter provided with the filter segment formed from the photosensitive coloring composition for organic EL display devices in any one of Claims 1-8 on a <9> transparent substrate.

<10> An organic EL display device comprising the color filter according to claim 9 and a white organic EL light source.

  The photosensitive coloring composition for organic EL display device of the present invention is highly sensitive even with a high pigment content, and has excellent linearity, pattern shape, and resolution of each color filter segment and black matrix in a wide film thickness. A photosensitive coloring composition suitable for an organic EL display device having development resistance and chemical resistance can be provided. Moreover, a high quality color filter can be obtained by using the photosensitive coloring composition for organic EL display devices of the present invention. Further, by using the color filter of the present invention, a high quality organic EL display device can be obtained.

FIG. 1 is an emission spectrum of the organic EL element (EL-1) used as a white light source.

<Photosensitive coloring composition for organic EL display device>
The photosensitive coloring composition of the present invention comprises a colorant (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an alkali-soluble resin (D), and a silane coupling agent (E). In the total solid content in the photosensitive coloring composition, the colorant (A) 42 to 60% by mass, the photopolymerizable compound (C) 15 to 35% by mass, the silane coupling agent (E) 0. 1 to 10% by mass, and the photopolymerizable compound (C) has at least one bond selected from the group consisting of a urethane bond and a bond derived from caprolactone modification in the molecule.

  Since the photosensitive coloring composition of the said structure has little dependence by the film thickness of a pattern shape, the wide use by various film thickness variations and hues is possible. Further, it is possible to form a filter segment and a black matrix having high sensitivity and excellent linearity, pattern shape, resolution, development resistance, and chemical resistance.

<Colorant (A)>
As the colorant (A) contained in the photosensitive coloring composition according to the embodiment of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Among the pigments, pigments having high color developability and high heat resistance are preferable, and organic pigments are usually used. Further, the colorant (A) can contain a dye within a range that does not lower the heat resistance.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition by embodiment of this invention is shown with a color index number.

[Organic pigments]
Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276, and the like. Among these, azo pigments, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, isoindoline-based, perinone-based, perylene-based, and benzimidazolone-based dyes are exemplified from the viewpoints of brightness and coloring power. Specifically, C.I. I. Pigment Red 176, 177, 179, 254, 242 and a naphthol azo pigment represented by the following general formula (1) are preferable. More preferably, it is a naphthol azo pigment represented by the following general formula (1). I. Pigment Red 269. By using the pigment, high coloring power can be obtained in the high color rendering color filter, the colorant component can be reduced, and the selection range of the resist formulation composition is widened.

General formula (1)

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

  Moreover, when using the photosensitive coloring composition of this invention as a red photosensitive composition, it is preferable to use a yellow pigment together with a red pigment.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, 231 and the quinophthalone pigment described in Japanese Patent No. 4993026. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment yellow 138, 139, 150, 185, 231.

  About this application, colorants other than a red pigment and a yellow pigment can be contained.

  Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, or 15: 6, and more preferably C.I. I. Pigment Blue 15: 6. Moreover, the aluminum phthalocyanine pigment etc. which are described in Unexamined-Japanese-Patent No. 2004-333817, 4893859 etc. can also be used, It is not limited to these in particular.

  Examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 Can be mentioned. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment Green 7, 36, 58, 59, 62, and 63. Moreover, the zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can also be used, and the invention is not particularly limited thereto.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

  Examples of the orange pigment include C.I. I. Pigment Orange 38, 43, 64, 71, or 73 is raised. Among these, from the viewpoint of brightness and coloring power, C.I. I. Pigment oranges 38, 43 and 64 are preferred.

  Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically C.I. I. Pigment Black 1, 6, 7, 12, 20, 31, etc. can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

  Inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments can be used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while balancing the saturation and lightness.

[Miniaturization of pigment]
When the colorant used in the photosensitive coloring composition of the present invention is a pigment, it is preferably 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. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult, and when the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. 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 mass, and most preferably 300 to 1000 parts by mass with respect to 100 parts by mass of the pigment in terms of both processing efficiency and 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 mass, and most preferably 50 to 500 parts by mass with respect to 100 parts by mass 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. It is preferable that the usage-amount of resin is the range of 5-200 mass parts with respect to 100 mass parts of pigments.

[dye]
The coloring composition by embodiment of this invention can also use dye as a coloring agent. As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes and the like can be used. Moreover, it may be in the form of lake pigments obtained by rake-forming these derivatives or dyes.

Furthermore, in the case of an acid dye having an acid group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, an inorganic salt of an acid dye, an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, use a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or salt formation using a resin component having these functional groups, or use as a salt-forming compound after sulfonamidation. Therefore, it is possible to obtain a colored composition having excellent fastness, which is preferable.
A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of excellent fastness. More preferably, the compound having an onium base is a resin having a cationic group in the side chain.

  In the case of a basic dye, it can be used after salt formation using an organic acid, perchloric acid or a metal salt thereof. A salt forming compound of a basic dye is preferable because of its excellent resistance and compatibility with a pigment, and further, a basic dye and an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound that is a counter component that works as a counter ion It is more preferable to use a salt-forming compound obtained by salting a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. Is.

Moreover, when it has a polymerizable unsaturated group in a pigment | dye frame | skeleton, it can be set as the dye excellent in tolerance, and it is preferable.
Moreover, when a dye has an oxetane group, the coloring composition containing this dye is excellent in the heat resistance after hardening. The dye having an oxetane group can be achieved, for example, by using an ethylenically unsaturated monomer having an oxetane structure in a resin constituting a salt-forming compound containing the dye.

  In one embodiment, the chemical structure of the dye includes, for example, azo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, Anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azines Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes Fee, perinone dyes, indigo dyes, mention may be made thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and a dye structure derived from a dye selected from those metal complex dyes.

  Among these pigment structures, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium from the viewpoint of color characteristics such as hue, color separation, and color unevenness Preferred are dye structures derived from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, phthalocyanine A pigment structure derived from a pigment selected from the system dyes is more preferable. For specific pigment compounds that can form a pigment structure, “New Edition Dye Handbook” (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), “Color Index” (The Society of Dyers and Colorists), “Dye Handbook” (Okawara et al.) Ed; Kodansha, 1986).

  Examples of the dye in another embodiment include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, methine dyes, diarylmethane dyes, triarylmethane dyes, Xanthene dye, thiazine dye, cationic dye, cyanine dye, nitro dye, quinoline dye, naphthoquinone dye, oxazine dye, perylene dye, diketopyrrolopyrrole dye, quinacridone dye, ansanthrone Examples include, but are not limited to, dyes, isoindolinone dyes, isoindoline dyes, indanthrone dyes, coumarin dyes, quinacridone dyes, pyranthrone dyes, flavanthrone dyes, and perinone dyes.

  Further, examples of the organic dye that can be used in another embodiment include triarylmethane, xanthene, and anthraquinone, and it is preferable to use xanthene.

[Xanthene dyes]
The xanthene dyes that can be preferably used are red and purple, and preferably have any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye. Moreover, it may be in the form of a lake pigment obtained by lacquering these dyes.
Among these, it is preferable to use a xanthene-based oil-soluble dye or a xanthene-based acid dye because of excellent hue.

Examples of red and purple colors include C.I. I. Solvent Red, C.I. I. Oil-soluble dyes such as solvent violet, C.I. I. Basic Red, C.I. I. Basic dyes such as basic violet, C.I. I. Acid Red, C.I. I. Acid dyes such as Acid Violet, C.I. I. Direct Red, C.I. I. Examples include those belonging to direct dyes such as direct violet.
Here, the direct dye has a sulfonic acid group (—SO ₃ H, —SO ₃ Na) in the structure, and in the present disclosure, the direct dye is regarded as an acid dye.

  Further, the xanthene basic dye is preferably used after being salted using an organic acid or perchloric acid. As the organic acid, organic sulfonic acid or organic carboxylic acid is preferably used. Of these, naphthalenesulfonic acid such as tobias acid and perchloric acid are preferably used in terms of resistance.

  In addition, xanthene-based acid dyes are used as salt-forming compounds by chlorination using quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, primary amine compounds, etc., or resin components having these functional groups. In view of resistance, it is preferable to use it as a sulfonamide compound after sulfonamidation.

  Salt forming compounds of xanthene acid dyes and / or sulfonic acid amide compounds of xanthene acid dyes are preferred because of their excellent hue and resistance, and quaternary ammonium which is a counter component that works as counter ions. It is more preferable to use a compound prepared by using a salt compound and a sulfonic acid amide compound obtained by sulfonamidating a xanthene acid dye.

  Among xanthene dyes, rhodamine dyes are preferable because they are excellent in color developability and resistance.

  Hereinafter, the form of the xanthene dye will be specifically described in detail.

[Xanthene oil-soluble dye]
Examples of xanthene oil-soluble dyes include C.I. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 42, C.I. I. Solvent Red 43, C.I. I. Solvent Red 44, C.I. I. Solvent Red 45, C.I. I. Solvent Red 46, C.I. I. Solvent Red 47, C.I. I. Solvent Red 48, C.I. I. Solvent Red 49, C.I. I. Solvent Red 72, C.I. I. Solven Red 73, C.I. I. Solvent Red 109, C.I. I. Solvent Red 140, C.I. I. Solvent Red 141, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent Violet 2, C.I. I. Solvent violet 10 and the like.
Among them, C.I., which is a rhodamine-based oil-soluble dye having high color developability. I. Solvent Red 35, C.I. I. Solvent Red 36, C.I. I. Solvent Red 49, C.I. I. Solvent Red 109, C.I. I. Solvent Red 237, C.I. I. Solvent Red 246, C.I. I. Solvent violet 2 is more preferable.

[Xanthene basic dye]
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Examples thereof include basic violet 10 (rhodamine B). Among these, C.I. I. Basic Red 1, C.I. I. It is preferable to use basic violet 10.

[Xanthene acid dyes]
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these, in particular, C.I., which is a rhodamine acid dye, is excellent in color developability, heat resistance and light resistance. I. Acid Red 52, C.I. I. Most preferably, Acid Red 289 is used.

The acid dye (not limited to xanthene) is preferably a salt-forming compound of an acid dye and a nitrogen-containing compound, such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, a primary amine compound, or the like. It is preferable to form a salt using a resin component having these functional groups to obtain a salt-forming compound of an acidic dye because high heat resistance, light resistance, and solvent resistance can be imparted. Acid dyes can impart high heat resistance, light resistance, and solvent resistance by sulfonamidation.
Further, it may be a salt-forming compound of an acid dye and a compound having an onium base, and among them, the compound having an onium base is a resin having a cationic group in the side chain, thereby reducing the lightness and resistance. It can be set as the outstanding coloring composition.

  Primary amine compounds include methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine (laurylamine), tridodecylamine, tetra Examples include aliphatic unsaturated primary amines such as decylamine (myristylamine), pentadecylamine, cetylamine, stearylamine, oleylamine, cocoalkylamine, beef tallow alkylamine, cured tallow alkylamine, allylamine, aniline, and benzylamine. .

  Secondary amine compounds include aliphatic unsaturated secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, diamylamine, diallylamine, methylaniline, ethylaniline, dibenzylamine, diphenylamine, dicocoalkyl. Amine, di-cured tallow alkylamine, distearylamine, etc.

  Examples of the tertiary amine compound include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, dimethylaniline, diethylaniline, tribenzylamine and the like.

(Quaternary ammonium salt compound)
When the organic dye used in the embodiment of the present invention is an acid dye, it is preferably used as a salt-forming compound (a) comprising an acid dye and a quaternary ammonium salt compound. A quaternary ammonium salt compound becomes an acid dye counter by having an amino group.

  A preferable form of the quaternary ammonium salt compound which is a counter component of the salt-forming compound (a) is colorless or white. Here, colorless or white means a so-called transparent state, and is defined as a state in which the transmittance is 95% or more, preferably 98% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Is. That is, it is preferably one that does not inhibit the color development of the dye component and does not cause a color change.

It is preferable that the molecular weight of the counter part which is a cation component of a quaternary ammonium salt compound is in the range of 190-900. Here, the cation moiety corresponds to the (NR ₁ R ₂ R ₃ R ₄ ) ⁺ moiety in the following general formula (5). When the molecular weight is smaller than 190, light resistance and heat resistance are lowered, and further, solubility in a solvent may be lowered. On the other hand, when the molecular weight is larger than 900, the ratio of the coloring component in the molecule is lowered, and the color developability is lowered and the lightness may be lowered. More preferably, the molecular weight of the counter portion is in the range of 240-850. Particularly preferred is a counter portion with a molecular weight in the range of 350-800. Here, the molecular weight was calculated based on the structural formula. The atomic weight of C was 12, the atomic weight of H was 1, and the atomic weight of N was 14.

  What is represented by the following general formula (5) may be used as a quaternary ammonium salt compound.

General formula (5)

[In General Formula (5), R _{1 to} R ₄ each independently represents an alkyl group having 1 to 20 carbon atoms or a benzyl group, and at least two of R _{1 to} R ₄ have 5 to 20 carbon atoms. It is. Y ^- is an anion of an inorganic or organic. ]

R ₁ to R ₄ of at least two or more carbon atoms by a 5 to 20, solubility in solvents is improved. When the number of alkyl groups having a carbon number of less than 5 is 3 or more, solubility in a solvent is deteriorated, and coating film foreign matter is likely to be generated. Further, if there is an alkyl group having more than 20 carbon atoms, the color forming property of the salt-forming compound (a) is impaired.

The Y ⁻ component constituting the anion may be an inorganic or organic anion, but is preferably a halogen, and is usually chlorine.

  The quaternary ammonium salt compounds include tetramethylammonium chloride, tetraethylammonium chloride, monostearyltrimethylammonium chloride, distearyldimethylammonium chloride, tristearylmonomethylammonium chloride, cetyltrimethylammonium chloride, trioctylmethylammonium chloride, dioctyldimethylammonium chloride. , Monolauryltrimethylammonium chloride, dilauryldimethylammonium chloride, trilaurylmethylammonium chloride, triamylbenzylammonium chloride, trihexylbenzylammonium chloride, trioctylbenzylammonium chloride, trilaurylbenzylammonium chloride Id, benzyl dimethyl stearyl ammonium chloride, and benzyl dimethyl octyl ammonium chloride, dialkyl (alkyl C14 -C18) dimethyl ammonium chloride (hydrogenated tallow), and the like.

  Specific examples of the quaternary ammonium salt compound products include, for example, Cotamin 24P, Cotamin 86P Conk, Cotamin 60W, Cotamin 86W, Cotamin D86P, Sanizole C, Sanizole B-50 manufactured by Kao Corporation, and Lion Corporation's Arcade 210- 80E, 2C-75, 2HT-75, 2HT flakes, 2O-75I, 2HP-75, 2HP flakes, and the like. Among them, Cotamine D86P (distearyldimethylammonium chloride), Arcard 2HT-75 (dialkyl (alkyl is C14- C18) dimethylammonium chloride).

(Resin having a cationic group in the side chain)
When the organic dye used in the embodiment of the present invention is an acid dye, it is also preferably used as a salt-forming compound (a ′) comprising an acid dye and a resin having a cationic group in the side chain. The resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) used in the embodiment of the present invention will be described.
The resin having a cationic group in the side chain for obtaining a salt-forming compound is not particularly limited as long as it has at least one onium base in the side chain, but a suitable onium salt structure is available. From the viewpoint of the above, ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable, and in consideration of storage stability (thermal stability), they are ammonium salts, iodonium salts, and sulfonium salts. It is more preferable. More preferred is an ammonium salt.

  When preparing a blue coloring composition for a color filter containing a salt-forming compound (a ′) and exhibiting the characteristics as a color filter, the same kind of resin as the binder resin constituting the blue coloring composition for the color filter is used. It is preferable to do. In one embodiment of the present invention, an acrylic resin is preferably used as the binder resin in the color filter coloring composition, and therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (a ′) is An acrylic resin is preferred.

  As the resin having a cationic group in the side chain, an alkali resin containing a structural unit represented by the following general formula (6) may be used. A salt-forming compound can be obtained when the cationic group in the general formula (6) forms a salt with the anionic group of the xanthene acid dye.

General formula (6)

[In General Formula (6), R ⁵¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ^{52 to} R ⁵⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R ^{52 to} R ⁵⁴ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group. Y ^- is an anion of an inorganic or organic. ]

Examples of the alkyl group for R ⁵¹ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ⁵¹ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ⁵¹ is most preferably a hydrogen atom or a methyl group.

In general formula (6), R ^{52 to} R ⁵⁴ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. Can be mentioned.

The ^alkyl group in R 52 ^{to R 52,} for example, straight-chain alkyl group (methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl, n- decyl, n- dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R ^{52 to} R ⁵⁴ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R ^{52 to} R ⁵⁴ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R ^{52 to} R ⁵⁴ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R ^{52 to} R ⁵⁴ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

Two of R ^{52 to} R ⁵⁴ may be bonded to each other to form a ring.

In general formula (6), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ⁵⁵ —, —COO—R ⁵⁵ —, and R ⁵⁵ represents an alkylene group, Among these, —CONH—R ⁵⁵ — and —COO—R ⁵⁵ — are preferable because of polymerizability and availability. R ⁵⁵ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (6) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; Carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

One method for introducing an oxetane group into a resin having a cationic group in the side chain is that the ethylenically unsaturated monomer containing an oxetane structure corresponds to the cationic group represented by the general formula (6). This is a method of copolymerizing with an ethylenically unsaturated monomer.
Examples of the ethylenically unsaturated monomer having an oxetane group include (3-methyl-3-oxetanyl) methyl (meth) acrylate, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, and (3-butyl-3 -Oxetanyl) methyl (meth) acrylate, (3-hexyltyl-3-oxetanyl) methyl (meth) acrylate, and the like.
Examples of commercially available products include ETERNACOLL OXMA (manufactured by Ube Industries), OXE-10, and OXE-30 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.).

(Salt formation)
A salt-forming compound of an acid dye and a nitrogen-containing compound or a resin having a cationic group in the side chain can be produced by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 11-72969.
For example, a xanthene acid dye may be used, and after the xanthene acid dye is dissolved in water, a quaternary ammonium salt compound may be added and subjected to chlorination while stirring. Here, the sulfonic acid group (—SO ₃ H) and sodium sulfonate group (—SO ₃ Na) in the xanthene acid dye and the ammonium group (NH ₄ ⁺ ) part of the quaternary ammonium salt compound are combined. A salt compound is obtained. In addition, instead of water, methanol and ethanol are also solvents that can be used for the chlorination.

Further, the salt-forming compound is obtained by stirring or vibrating an aqueous solution in which a resin having a cationic group in the side chain represented by the general formula (6) and an acidic dye are dissolved, or represented by the general formula (6). It can be easily obtained by mixing an aqueous solution of a resin having a cationic group in the side chain and an aqueous solution of an acidic dye under stirring or vibration. In the aqueous solution, the ammonium group of the resin and the anionic group of the acidic dye are ionized and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. As for the resin having a cationic group in the side chain to be used and the acid dye, only a single type or a plurality of types having different structures may be used.
In addition, with other acidic dyes, a salt-forming compound with a nitrogen-containing compound or a resin having a cationic group in the side chain can be obtained in the same manner as the xanthene dye.

(Sulphonic acid amide compound)
The acidic dye may be a sulfonic acid amide compound obtained by reacting a sulfonic acid amide compound with an anionic dye.
A sulfonic acid amide compound of an acid dye that can be preferably used for an acid dye is obtained by chlorinating an acid dye having —SO ₃ H and —SO ₃ Na by a conventional method to convert —SO ₃ H to —SO ₂ Cl. Compounds can be prepared by reacting with amines having —NH ₂ groups.
Specific examples of amine compounds that can be preferably used in sulfonamidation include 2-ethylhexylamine, dodecylamine, 3-decyloxypropylamine, 3- (2-ethylhexyloxy) propylamine, and 3-ethoxypropyl. It is preferable to use amine, cyclohexylamine or the like.
An example using a xanthene acid dye is C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 289 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 289 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 289.
In addition, C.I. I. In the case of obtaining a sulfonic acid amide compound obtained by modifying Acid Red 52 with 3- (2-ethylhexyloxy) propylamine, C.I. I. Acid Red 52 was converted to a sulfonyl chloride and reacted with a theoretical equivalent of 3- (2-ethylhexyloxy) propylamine in dioxane to give C.I. I. What is necessary is just to obtain the sulfonic acid amide compound of Acid Red 52.
Moreover, also in other acidic dyes, a sulfonic acid amide compound can be obtained in the same manner as xanthene dyes.

  As the xanthene-based dyes, JP2010-032999A, JP2011-138094A, JP2011-227313A, JP2011-242752A, JP2012-107192A, JP2013-103A. No. 033194, Japanese Patent Application No. 2011-71888, Japanese Patent Application No. 2013-72263, Japanese Patent Application No. 2013-81209, Japanese Patent Application Laid-Open No. 2014-173064, Japanese Patent Application No. 2013-53028, Japanese Patent Application No. 2013-52186 JP, 2014-196392, JP 2014-196393, JP 2014-201714, JP 2014-201715, JP 2013-050693, JP 2013-178478, JP2013-203156A, International It may be a known technique described in Hirakidai 2013/011687 pamphlet or the like.

  In one embodiment, xanthene dyes include C.I. I. Acid Red 51, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B, Acid Rhodamine G, C.I. I. Acid Violet 9, C.I. I. Acid Violet 9, C.I. I. It is preferable to use Acid Violet 30. Among them, C.I. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. It is preferable to use Acid Red 388.

[Dipyrromethene dye]
The dipyrromethene dye is a dye having a partial structure derived from a dipyrromethene dye as a partial structure of the dye part, and preferably a dipyrromethene compound and a dipyrromethene metal complex compound obtained from a dipyrromethene compound and a metal or a metal compound. A metal complex compound in which the structure represented by the general formula (7) is coordinated to a metal atom or a metal compound (hereinafter, appropriately referred to as “dipyrromethene metal complex compound”) is preferable.

[Dipyrromethene metal complex compound]
The metal complex compound (dipyrromethene metal complex compound) in which the structure represented by the general formula (7) is coordinated to a metal atom or a metal compound will be described.

General formula (7)

[In General Formula (7), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a monovalent substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic ring. Represents a group. ]

The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be any divalent metal atom, divalent metal oxide, divalent metal hydroxide, or 2 Valent metal chlorides are included. Examples of the metal or metal compound include ZnCl, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, and B, as well as AlCl ₃ , InCl ₃ , and FeCl. ₃ , metal chlorides such as TiCl ₂ , SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, as a metal or a metal compound, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, and the like from the viewpoint of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, and the like. Ni, Co, TiO, B, or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO is most preferred.

  Examples of such dipyrromethene dyes include JP-A-2008-292970, JP-A-2010-85758, JP-A-2010-84009, Japanese Patent Application No. 2010-43530, JP-A-2013-080010, Known techniques described in Japanese Unexamined Patent Publication No. 2013-210596 and International Publication No. 2013/141156 can be used.

[Triphenylmethane dye]
Examples of the triphenylmethane dye skeleton include a diaminotriphenylmethane dye skeleton, a triaminotriphenylmethane dye skeleton, and a rosic acid dye skeleton having an OH group.
Triaminotriphenylmethane-based dye skeletons are preferable in that they are excellent in color tone and more excellent in fastness to sunlight than others. Among them, a diphenylnaphthylmethane dye skeleton that is a basic dye is particularly preferable.

[Triphenylmethane basic dye]
The triphenylmethane-based basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminoarylmethane-based basic dye is preferable in terms of good blue, red and green coloring.
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a vivid color tone and is preferable because it is more excellent in fastness to sunlight than other dyes.

  Since the blue triphenylmethane basic dye has a spectral characteristic having a high transmittance at 400 to 440 nm, it can have high brightness, particularly when used for forming a blue filter segment. This is preferable because it is possible.

Specific examples of triphenylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Examples include Basic Green 1 (Brilliant Green GX) and 4 (Malachite Green).
Above all, from the point of brightness, C.I. I. It is preferable to use Basic Blue 7.

  Further, in the case of a triphenyl basic dye, it can be used after being salted using an organic acid, perchloric acid or a metal salt thereof. Among them, a salt forming compound of a basic dye is preferable because of its resistance and excellent compatibility with pigments, and further, a basic dye and organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus, which are counter components that function as counter ions. It is possible to use a salt-forming compound obtained by salting an anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

  Specifically, organic acids such as heteropoly acids, organic sulfonic acids such as aliphatic sulfonic acids and aromatic sulfonic acids, organic sulfuric acids such as aliphatic sulfuric acids and aromatic sulfuric acids, organic carboxylic acids such as aromatic carboxylic acids and fatty acids, Or it has the form of an acid dye. Alternatively, a metal salt thereof may be used. A salt-forming compound with a resin having an acid group is also preferable.

(Salt formation)
These salt forming compounds of a basic dye and an anionic counter can be synthesized by a conventionally known method. A specific method is disclosed in Japanese Patent Laid-Open No. 2003-215850.
For example, after the triarylmethane basic dye is dissolved in water, an organic sulfonic acid or (sodium organic sulfonate) solution may be added and subjected to chlorination treatment while stirring. Here, a salt-forming compound in which the amino group (—NHC ₂ H ₅ ) portion in the triarylmethane-based basic dye and the sulfonic acid group (—SO ₃ H) portion of the organic sulfonic acid are bonded is obtained.
Here, the organic sulfonic acid can be dissolved in an alkali solution such as sodium hydroxide before the salt-forming treatment and used as a form of sodium sulfonate (—SO ₃ Na). In the present disclosure, a sulfonic acid group (—SO ₃ H) and a functional group (—SO ₃ Na) that is sodium sulfonate may be referred to without distinction.

  Examples of such triphenylmethane dyes include JP-A No. 2002-014222, JP-A No. 2003-246935, JP-A No. 2003-246935, JP-A No. 2008-304766, and JP-A No. 2010-256598. Japanese Patent Application No. 2011-200560, Japanese Unexamined Patent Application Publication No. 2011-186043, Japanese Unexamined Patent Application Publication No. 2012-173399, Japanese Unexamined Patent Application Publication No. 2012-233303, Japanese Unexamined Patent Application Publication No. 2012-098522, Japanese Patent Application No. 2012-288970, Known techniques described in Japanese Patent Application No. 2012-200469, Japanese Patent Application Laid-Open No. 2014-196262, International Publication No. 2010/123071, Pamphlet of International Publication No. 2011/162217, International Publication No. 2013/108591, etc. Use It can be.

  In one embodiment, the triphenylmethane dye includes C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 19, C.I. I. Acid Violet 21, C.I. I. Acid Violet 24, C.I. I. Acid Violet 25, C.I. I. Acid Violet 38, C.I. I. Acid Violet 49, C.I. I. Acid Blue 1, C.I. I. Acid Blue 3, C.I. I. Acid Blue 5, C.I. I. Acid Blue 7, C.I. I. Acid Blue 9, C.I. I. Acid Blue 11, C.I. I. Acid Blue 13, C.I. I. Acid Blue 15, C.I. I. Acid Blue 17, C.I. I. Acid Blue 22, C.I. I. Acid Blue 24, C.I. I. Acid Blue 26, C.I. I. Acid Blue 75, C.I. I. Acid Blue 83, C.I. I. Acid Blue 90, C.I. I. Acid Blue 93, C.I. I. Acid Blue 100, C.I. I. Basic Blue 81, C.I. I. It is preferable to use Basic Blue 83.

  Alternatively, as a triarylmethane dye, C.I. I. Basic Violet 1, C.I. I. Basic Violet 2, C.I. I. Basic Violet 3, C.I. I. Basic Violet 4, C.I. I. Basic Violet 14, C.I. I. Basic Blue 1, C.I. I. Basic Blue 5, C.I. I. Basic Blue 7, C.I. I. Basic Blue 11, C.I. I. Basic blue 26 can be preferably used.

[Cyanine dyes]
Any cyanine dye can be used without limitation as long as it is a compound having a dye moiety containing a cyanine skeleton in the molecule.
Examples of cyanine dyes include C.I. I. Basic yellow 11, 12, 13, 14, 21, 22, 23, 24, 28, 29, 33, 35, 40, 43, 44, 45, 48, 49, 51, 52, 53, C.I. I. Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66, 68, C.I. I. Basic violet 7, 15, 16, 20, 21, 39, 40, C.I. I. Basic orange 27, 42, 44, 46, C.I. I. Basic blue 62, 63, etc. may be mentioned.
In addition, cyanine dyes described in JP2014-224970A, JP2013-261614A, and the like can also be used.

[Anthraquinone dyes]
An anthraquinone dye is a dye having an anthraquinone skeleton in the molecule.
Examples of the anthraquinone dye include C.I. I. Solvent Yellow 117, 163, 167, 189, C.I. I. Solvent Orange 77, 86, C.I. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247, C.I. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60, C.I. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139, C.I. I. Solvent Green 3, 28, 29, 32, 33, C.I. I. Acid Red 80, C.I. I. Acid Green 25, 27, 28, 41, C.I. I. Acid Violet 34, C.I. I. Acid Blue 25, 27, 40, 45, 78, 80, 112, C.I. I. Disperse Yellow 51, C.I. I. Disperse violet 26, 27, C.I. I. Disperse Blue 1, 14, 56, 60, C.I. I. Direct Blue 40, C.I. I. Modern Red 3, 11, C.I. I. Modern Blue 8 etc. are mentioned. Further, anthraquinone dyes described in JP-A-9-291237, WO2003 / 080734, WO2006 / 024617, JP2011-174987, JP2013-53273, and the like are used. It can be used as a known technique. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye. As an anthraquinone dye, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 45, C.I. I. Acid Blue 80, C.I. I. Solvent Blue 104, and C.I. I. Solvent blue 122 is preferable from the viewpoint of brightness and contrast.

  In one embodiment, as an anthraquinone dye, C.I. I. Acid Violet 29, C.I. I. Acid Violet 31, C.I. I. Acid Violet 33, C.I. I. Acid Violet 34, C.I. I. Acid Violet 36, C.I. I. Acid Violet 39, C.I. I. Acid Violet 43, C.I. I. Acid Violet 48, C.I. I. Acid Violet 63, C.I. I. Acid Violet 109, C.I. I. Acid Blue 25, C.I. I. Acid Blue 27, C.I. I. Acid Blue 41, C.I. I. Acid Blue 45, C.I. I. Acid Blue 62, C.I. I. Acid Blue 80, C.I. I. Acid Blue 127, C.I. I. Acid Blue 129, C.I. I. Acid Blue 145, C.I. I. Acid Blue 225, C.I. I. Acid Blue 230, C.I. I. Acid Blue 260, C.I. I. Acid Blue 264, C.I. I. Acid Blue 277, C.I. I. Acid Blue 281, C.I. I. Acid Blue 324, or C.I. I. It is preferable to use Acid Blue 350.

  In recent years, it is necessary to increase the content of the colorant in the photosensitive coloring composition in order to improve the color reproduction characteristics and reduce the thickness of the color filter. When used for an organic EL display device, the content of the colorant (A) is 42% by mass or more and 60% by mass or less in 100% by mass of the solid content of the photosensitive coloring composition for color filter according to the embodiment of the present invention. is there. If it is more preferably 44% by mass, particularly preferably 46% by mass or more, sufficient color reproducibility can be obtained, and the film thickness can be reduced. Further, if it is more preferably 57% by mass or less, particularly preferably 55% by mass or less, the content of the resin or photopolymerizable compound as the curable material becomes appropriate, and a sufficient cured coating film can be obtained.

<Photoinitiator (B)>
The photosensitive coloring composition of this invention contains a photoinitiator (B). With the photopolymerization initiator (B), the photosensitive composition can be cured by ultraviolet irradiation, and a filter segment can be formed by a photolithography method.

As photopolymerization initiator (B), 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 Or benzoin compounds 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- Thioxanthone compounds such as diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-me Xylphenyl) -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) phenyl-, 2- (O-benzoy Oxime)], or oxime ester compounds such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as 2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone A borate compound; a carbazole compound; an imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
Commercially available acetophenone compounds are all manufactured by BASF Corporation, “IRGACURE 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one), “IRGACURE 369”. (2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone), “IRGACURE 379” 2-benzyl-2-dimethyl As amino-1- (4-morpholinophenyl) -butan-1-one and a phosphine compound, all manufactured by BASF “IRGACURE 819” (bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide), “IRGACURE TPO” (2,4,6-trimethylbenzoyldiphenylphos In'okisaido), and the like.

  The photopolymerization initiator (B) contained in the photosensitive coloring composition of the present invention is particularly preferably an oxime ester compound represented by the general formula (2).

General formula (2)

[In General Formula (2), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, substituted or Unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl Represents a group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ]

The hydrogen atom of the substituent in R _{1 to} R ₄ described above may be further substituted with another substituent. Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyla Alkyl groups such as alkyl groups, dimethylamino groups, diethylamino groups, morpholino groups, piperidino groups and other dialkylamino groups, phenylamino groups, p-tolylamino groups and other arylamino groups, methyl groups, ethyl groups, tert-butyl groups Alkyl groups such as dodecyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, benzofuranyl groups, etc., aryl groups, furyl groups, thienyl groups, etc. Others, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, Phosphono group, trimethylammonium group, dimethylsulfo group Umiru group, triphenyl phenacyl phosphonium Niu mill group, and the like.

In general formula (2), preferably, R ₁ is a substituted or unsubstituted alkyl group, R ₂ and R ₃ are hydrogen atoms, and R ₄ is a substituted or unsubstituted heterocyclic group or a substituted or unsubstituted group. Of the aryl group.

The most preferable structure includes compounds represented by the following formulas (3) and (4).
Formula (3)

Formula (4)

  Oxime ester-based photopolymerization initiators are believed to decompose the oxime ester moiety by absorbing ultraviolet rays to produce iminyl radicals and alkyloxy radicals, and the radicals of the active species produced by further decomposition cause the reaction. However, since the photopolymerization initiator contained in the photosensitive coloring composition has a structure represented by the general formula (2), the decomposition efficiency by ultraviolet irradiation is very high, and the pattern can be obtained with a small exposure amount. Can be formed.

  The reason why the photopolymerization initiator that can be preferably used in the present invention can function with higher sensitivity than the conventional initiator is considered as two possible reasons, but the details are not clear.

  The first reason is that the photopolymerization initiator (B) of the present invention has extremely high ultraviolet absorption performance due to the structure represented by the general formula (2), so that the energy of the given energy beam is extremely high. It can absorb well. Furthermore, it is conceivable that the obtained energy is efficiently used for the decomposition of the oxime ester moiety, so that the decomposition by the energy beam irradiation is fast and a large amount of radicals can be generated instantaneously.

The second reason is that the photopolymerization initiator (B) of the present invention has a structure represented by the general formula (2), in which decomposition of an iminyl radical generated by absorbing ultraviolet rays into a radical of an active species is represented by It can be considered that it is very fast. If the iminyl radical to be produced is metastable, the decomposition is slowed down and the amount of active radicals produced is reduced, but this is greatly affected by the chemical structure of the UV-absorbing moiety. The photopolymerization initiator (B) of the present invention has a structure represented by the general formula (2), so that the iminyl radical generated by the decomposition by light irradiation is decomposed very quickly, and a large amount of radicals are generated. It is thought that it has brought.
Moreover, since the photoinitiator (B) of this invention decomposes | disassembles iminyl radical very rapidly as mentioned above, it is possible that recombination is suppressed. When the number of recombination is large, the active species generated by the decomposition is reduced, so that the function as a radical polymerization initiator is lowered.

  The photopolymerization initiator (B) represented by the general formula (2) is preferably 0.1 to 50 parts by weight, particularly preferably 100 parts by weight of the colorant (A) in the photosensitive coloring composition. Can be used in an amount of 0.1 to 30 parts by mass.

<Sensitizer>
Furthermore, the photosensitive coloring composition according to the embodiment of the present invention can contain a sensitizer. The content of the sensitizer can be used in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (B) in the photosensitive coloring composition.

  Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by 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, Michler's ketone derivatives and the like.

  Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the compound represented by the general formula (2) include thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- N-ethylcarbazole or the like can be used.
The sensitizer may contain two or more sensitizers in any ratio.

<Photopolymerizable compound (C)>
The photosensitive coloring composition of this invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) in the present invention has at least one bond selected from the group consisting of a urethane bond and a bond derived from caprolactone modification in at least the molecule.

(Polymerizable compound having urethane bond)
The polymerizable compound having a urethane bond in the present invention is a photopolymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane obtained by reacting a polyfunctional isocyanate with an alcohol and further reacting a (meth) acrylate having a hydroxyl group. Examples thereof include urethane acrylate.

  Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri ( (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide modified penta (meth) acrylate, dipentaerythritol propylene oxide modified penta (meth) acrylate, dipentaerythritol caprolactone modified penta (meth) acrylate, glycerol acrylate Methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, containing epoxy groups The reaction product of compound and the carboxy (meth) acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

  Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

  Moreover, although there is no restriction | limiting in the structure of alcohol, when a polyhydric alcohol is used, since the crosslinking degree of a cured coating film becomes high and coating-film resistance goes up, it is preferable. Examples of the polyhydric alcohol include propylene glycol, ethylene glycol, glycerin, trimethylolpropane, and pentaerythritol.

  As these commercial products, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167, manufactured by Kyoeisha Chemical Co., Ltd., manufactured by Shin-Nakamura Chemical Co., Ltd. UA-160TM, UV-4108F manufactured by Osaka Organic Chemical Industry Co., Ltd., UV-4117F, and the like can be suitably used.

(Polymerizable compound having a bond derived from caprolactone modification)
The polymerizable compound having a bond derived from caprolactone modification in the present invention may contain a photopolymerizable compound having a bond derived from caprolactone modification. Examples include caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified trimethylolpropane triacrylate, and the like. Examples of commercially available products include KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, and KAYARAD DPCA-120 manufactured by Nippon Kayaku.

  The photopolymerizable compound (C) of the present invention can be used by mixing known photopolymerizable compounds other than those described above. Examples of known photopolymerizable compounds other than the above include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 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, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (Meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, trimethylolpropane PO modified tri (meth) acrylate Trimethylolpropane EO modified tri (meth) acrylate, isocyanuric acid EO modified di (meth) acrylate, isocyanuric acid EO modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether 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, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated Various acrylic and methacrylic esters such as (meth) acrylic ester of lamin, epoxy (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, Esterified products of poly (meth) acrylates containing free hydroxyl groups of polyhydric alcohols and (meth) acrylic acids, such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, and dicarboxylic acids A polymerizable compound having an acid group such as an esterified product of a polyvalent carboxylic acid and a monohydroxyalkyl (meth) acrylate is exemplified, but is not necessarily limited thereto.

  Examples of these commercially available products include KAYARAD R-128H, KAYARAD R526, KAYARAD PEG400DA, KAYARAD MAND, KAYARD NPGDA, KAYARAD R-167, KAYARAD HX-220, KAYARAD R-551, KAYARAD R121, KAYARAD R121, -604, KAYARAD R-684, KAYARAD GPO-303, KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPEA-12, KAYAARAD DPHA-2C, KAYARAD D-310, KAYAARAD D-330, and Aronix M manufactured by Toagosei M M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-36 M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M -101A, M-5300, M-5400, M-5700, M-510, M-520 Made by Osaka Organic Chemical Co., Ltd. Biscoat # 310HP, Biscoat # 335HP, Biscoat # 700, Biscoat # 295, Biscoat # 330, Biscoat # 360 Biscoat #GPT, biscoat # 400, biscoat # 405, biscoat # 2500P, NK ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like can be preferably used.

  The compounding quantity of a photopolymerizable compound (C) is 15-35 mass parts on the basis of the total solid content of a photosensitive composition (100 mass parts). From a viewpoint of photocurability and developability, it is preferably 17 to 30 parts by mass. If the amount is less than 15 parts by mass, the height of the formed coating film is insufficient, and the change of the line width during patterning due to the development time becomes large. On the other hand, when the amount is more than 35 parts by mass, the alkali developability is inferior and the pattern linearity during patterning is inferior.

<Alkali-soluble resin (D)>
The photosensitive coloring composition of this invention contains alkali-soluble resin (D) from a developable viewpoint. The alkali-soluble resin (D) is for imparting development solubility in an alkali development step at the time of producing a color filter, and has an acid group and / or a hydroxyl group. The alkali-soluble resin (D) has a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm. Alkali-soluble resins (D) include thermoplastic energy, thermosetting resin, active energy ray curable resin having an ethylenically unsaturated double bond, etc. when classified according to the main curing method, and active energy ray curable. The resin may be a thermoplastic resin or may have a thermosetting function. Moreover, you may include the thermoplastic resin which is not active energy ray hardening. These can be used alone or in admixture of two or more.

<Thermoplastic resin>
Examples of the thermoplastic resin that can be used as the alkali-soluble resin (D) include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and 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, And polyimide resin.
In order to make the thermoplastic resin soluble in alkali, for example, it has an acidic group such as a carboxyl group or a sulfone group. Specific examples of the 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 isobutylene / And (anhydrous) maleic acid copolymer. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an alkali-soluble resin having an acidic group and / or a hydroxyl group, has developability, heat resistance, and transparency. Since it is high, it is preferably used.

<Alkali-soluble resin having an ethylenically unsaturated double bond>
The alkali-soluble resin contained in the photosensitive coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond is introduced by the following methods (i) and (ii), the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the crosslink density is increased and the chemical resistance is improved.

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

  Examples of the ethylenically unsaturated 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 be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

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

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
Or hydroxyalkyl methacrylates such as 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. May be used in combination. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol mono (meth) acrylate is preferable. From the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. Glycerol mono (meth) acrylate is more preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [methacryloyloxy] ethyl isocyanate, and the like. However, two or more types can be used in combination without being limited to these.

  The following are mentioned as a monomer which comprises alkali-soluble resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene (Meth) acrylates such as lenglycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, dye (Meth) acrylamides such as acetone (meth) acrylamide or acryloylmorpholine styrene, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether And fatty acid vinyls such as vinyl acetate or vinyl propionate.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl ] N-substituted maleimides such as maleimide and 9-maleimide acridine, compounds represented by the following general formula (8), specifically EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylation Phenyl acrylate, phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, nonylphenol EO modification (Meth) acrylate, PO-modified (meth) acrylate of nonylphenol and the like.

General formula (8)

(In General Formula (8), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon that may have a benzene ring. (It is an alkyl group of the number 1-20, and n is an integer of 1-15.)

  A carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

  Moreover, a hydroxyl-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. And hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Also, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate added with (poly) 12-hydroxystearic acid and the like.

  A phosphoric ester group-containing ethylenically unsaturated monomer can also be used. As the phosphoric ester group-containing ethylenically unsaturated monomer, for example, a monomer that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Is mentioned.

<Alkali-soluble resin having no ethylenically unsaturated double bond>
The photosensitive coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film. By synthesizing at least one kind of carboxyl group-containing ethylenically unsaturated monomer and one or more other ethylenically unsaturated monomers, and by not giving an ethylenically unsaturated bond to the side chain, It is possible to obtain an alkali-soluble resin that does not have a polymerizable unsaturated double bond.

The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, in order to impart alkali development solubility. More preferable is 20,000 or less. Moreover, it is preferable that the value of Mw / Mn is 10 or less. When the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate is lowered, and the exposed pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.
The acid value of the alkali-soluble resin in the present invention is from 30 to 200 (KOHmg / g) in order to impart alkali development solubility, preferably in the range of 40 to 180, more preferably 50 to 170. It is a range. When the acid value is less than 30, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesiveness to the substrate is lowered, and the exposure pattern is hardly left.

  The content of the binder resin (D) in the photosensitive coloring composition of the present invention is preferably 5 to 100 parts by mass, more preferably 10 to 90 parts by mass based on the total weight of the colorant (100 parts by mass). It is. It is preferably used in an amount of 5 parts by mass or more because the film formability and various resistances are good, and it is preferably used in an amount of 100 parts by mass or less because the colorant concentration is high and good color characteristics can be expressed. .

<Epoxy compound>
The photosensitive composition of the present invention can contain an epoxy compound. As an epoxy compound to be used, a known compound having an epoxy group can be used without particular limitation.

Epoxy compounds include phenol novolac type epoxy resin, cresol novolac type epoxy resin, trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, biphenol type epoxy. Examples thereof include resins, bisphenol-A novolac type epoxy resins, naphthalene skeleton-containing epoxy resins, alicyclic epoxy resins, and heterocyclic epoxy resins.
Among these, it is preferable that the epoxy compound is an alicyclic epoxy resin from the viewpoint of improvement of water spots or heat resistance and chemical resistance.

  Specific examples of the phenol novolac type epoxy resin include, for example, Epicron N-740, Epicron N-770, Epicron N-775 manufactured by DIC Corporation, and D.C. E. N438, Nippon Kayaku Co., Ltd. RE-306, Mitsubishi Chemical Corporation jER152, jER154, etc. are mentioned.

  Specific examples of the cresol novolac type epoxy resin include Epicron N-660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, and Epicron N-665 manufactured by DIC Corporation. EXP, Epicron N-672-EXP, Nippon Kayaku Co., Ltd. EOCN-102S, EOCN-103S, EOCN-104S, Union Carbide Corporation UVR-6650, Sumitomo Chemical Co., Ltd. ESCN-195 etc. are mentioned.

  Specific examples of the trishydroxyphenylmethane type epoxy resin include Nippon Kayaku Co., Ltd. EPPN-503, EPPN-502H, EPPN-501H, Dow Chemical Co., Ltd. TACTIX-742, Mitsubishi Chemical Co., Ltd. jER E1032H60, etc. Can be mentioned.

  Specific examples of the dicyclopentadiene phenol type epoxy resin include Epicron EXA-7200 manufactured by DIC Corporation, and TACTIX-556 manufactured by Dow Chemical Co., Ltd.

  Specific examples of the bisphenol type epoxy resin include jER828 and jER1001 manufactured by Mitsubishi Chemical Corporation, UVR-6410 manufactured by Union Carbide Corporation, and D.C. E. Bisphenol-A type epoxy resin such as R-331, YC-8125 manufactured by Nippon Kayaku Manufacturing Co., Ltd., UVR-6490 manufactured by Union Carbide Co., Ltd., YDF-8170 manufactured by Nippon Kayaku Manufacturing Co., Ltd. An epoxy resin etc. are mentioned.

  Specific examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H manufactured by Nippon Kayaku Co., Ltd., and bixylenol type epoxy such as jER YX-4000 and jER YL-6121 manufactured by Mitsubishi Chemical Corporation. Examples thereof include resins.

  Specific examples of the bisphenol A novolac type epoxy resin include Epicron N-880 manufactured by DIC Corporation, jER E157S75 manufactured by Mitsubishi Chemical Corporation, and the like.

  Specific examples of the naphthalene skeleton-containing epoxy resin include NC-7000 and NC-7300 manufactured by Nippon Kayaku Co., Ltd., EXA-4750 manufactured by DIC Corporation, and the like.

  Specific examples of the alicyclic epoxy resin include Seikeside 2021P, 2081, 2000, Epolide PB3600, PB4700, GT401, EHPE-3150, and Cyclomer M100 manufactured by Daicel Corporation.

  Specific examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S manufactured by Nissan Chemical Industries, Ltd.

  These epoxy compounds can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Content of the epoxy compound used for the coloring composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. When the content of the epoxy compound is in the above range, heat resistance is high and an excellent coating film is obtained, which is preferable.

<Oxetane compound>
The photosensitive composition of the present invention preferably contains an oxetane compound. As the oxetane compound, a known compound having an oxetane group is not particularly limited and can be used. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or more.

Monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl- 3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- ( Triethoxysilyl) propoxy] methyl} oxetane and the like.
Specific examples include OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXE-30 manufactured by Toagosei Co., Ltd., OXT-101, 212, and the like.

Examples of the bifunctional oxetane group include 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Benzene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3- Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3- Til-3-oxetanylmethoxy) methyl] propane, ethyleneglycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethyleneglycolbis (3-ethyl) -3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl) -3-Oxetanylmethoxy) hexane, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bis Enol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ) Ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, and the like.
Specific examples include Ube Industries, Ltd., OXBP, OXTP, Toagosei Co., Ltd., OXT-121, OXT-221, and the like.

As an oxetane group having two or more functional groups,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, oxy Resin (e.g., Patent No. 3,783,462 No. oxetane-modified phenol novolak resin according) containing Tan group or above, such as OXE-30 (meth) polymers obtained by the acrylic monomer by radical polymerization. Such a polymer can be obtained using a known polymerization method.

  Content of the oxetane compound used for the photosensitive composition of this invention is 0.5-50 mass% normally in 100 mass% of solid content of a coloring composition, Preferably it is 1-40 mass%. It is preferable for the content of the oxetane compound to be in the above range since an excellent coating film having good water spots and high chemical resistance can be obtained.

<Silane coupling agent (E)>
The photosensitive coloring composition by embodiment of this invention contains a silane coupling agent (E). By the silane coupling agent (E), the adhesion to the transparent substrate is improved, the reproducibility of fine lines is improved, and the resolution is improved.
Examples of the silane coupling agent include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxy (Cyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-amino Propyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, Examples include aminosilanes such as N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

  As the silane coupling agent (E) in the present application, one containing a reactive unsaturated double bond is particularly preferable. By having a reactive double bond in the silane coupling agent, it becomes possible to provide adhesion while maintaining the fringe formation sensitivity at the substrate-coating boundary during development, and the fringe shape pattern linear It has good properties, and there are no undercuts or chips in the pattern.

  Content of a silane coupling agent is 0.1-10 mass% with respect to the total solid in a photosensitive coloring composition, More preferably, it is 0.3-0.7 mass%.

<Antioxidant (F)>
The photosensitive coloring composition according to the embodiment of the present invention may 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, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the embodiment of the present invention may be a compound having an ultraviolet absorption function, a radical scavenging function, or a peroxide decomposition function, and specifically, a hindered phenol type as an antioxidant. Hindered amine, phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylate, and triazine compounds, and known ultraviolet absorbers and antioxidants 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. Further, a hindered phenol antioxidant, a hindered amine antioxidant, or a phosphorus antioxidant is more preferable, and a hindered phenol antioxidant is particularly preferable. These antioxidants can be used singly or as a mixture of two or more at any ratio as required.

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

  Specific examples include ADEKA Corporation ADK STAB AO-20, AO-30, AO-40, AO50, AO60, AO80, AO320, Chemipro Corporation KEMINOX 101, 179, 76, 9425, BASF Corporation IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sun Chemical Co., Ltd. Syanox CY-1790, CY-2777, and the like.

  The content of the antioxidant is more preferably 0.2 to 5.0% by mass based on the solid content weight of the photosensitive coloring composition because the brightness and sensitivity are good.

<Polymerization inhibitor (G)>
The photosensitive coloring composition according to the embodiment of the present invention may contain a polymerization inhibitor (G) in order to prevent exposure by diffracted light from the mask during exposure. By containing the polymerization inhibitor (G), the shape and resolution of the pattern can be controlled. Examples of the polymerization inhibitor include hydroquinone such as methyl hydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol. Derivatives and phenol compounds, amine compounds such as phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. And manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine, etc. Toroso compounds and their ammonium salts or aluminum salts and the like, used alone or in combination.

  And the polymerization inhibitor (G) can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant (A) in the coloring composition. . Can obtain better resolution by using 0.01 parts by mass or more of the polymerization inhibitor (G).

<Multifunctional thiol (H)>
The photosensitive coloring composition by embodiment of this invention can contain polyfunctional thiol (H). The polyfunctional thiol (H) is a compound having two or more thiol (-SH) groups.
When the polyfunctional thiol (H) is used together with the above-described photopolymerization initiator (B), a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated in the radical polymerization process after light irradiation. The resulting photosensitive coloring composition has high sensitivity. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable.
For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tris Thioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), Pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol Hexhexakis (3-mercaptopropionate), 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 individually by 1 type or in mixture of 2 or more types.

As for content of polyfunctional thiol (H), 0.05-100 mass parts is preferable with respect to 100 mass parts of coloring agents (A), More preferably, it is 1.0-50.0 mass parts.
By using 0.05 part by mass or more of polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Ultraviolet absorber>
The photosensitive composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds. .

  As for content of a ultraviolet absorber, 5-70 mass% is preferable in a total of 100 mass% of a photoinitiator and a ultraviolet absorber. When the content of the UV absorber is less than the above, the effect of the UV absorber is small and the resolution cannot be ensured. When the content is more than the above, the sensitivity is low and the pixel peeling or the hole diameter is larger than the design value. In some cases, such a problem may occur.

  At this time, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

  Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, the adhesion is weakened and pixel peeling occurs, and if it is more than the above, the sensitivity may be too high and the resolution may deteriorate.

  At this time, when the photosensitive composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

  Examples of the benzotriazole-based organic compound include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, and octyl-3 [3-tert-butyl. -4-hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H) -Benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-tbutyl- 5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2 Hydroxyphenyl) benzotriazole, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3- (2H— Benzotriazol-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compounds, 2- (2H-benzotriazol-2-yl) -4,6 -Bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3) -Tetramethylbutyl) phenol.

  More specifically, “TINUVIN P”, “TINUVIN PS”, “TINUVIN 109”, “TINUVIN 234”, “TINUVIN 326”, “TINUVIN 328”, “TINUVIN 329”, “TINUVIN 360”, “TINUVIN 360”, “TINUVIN 360”, “TINUVIN 360” TINUVIN 384-2 "," TINUVIN 900 "," TINUVIN 928 "," TINUVIN 99-2 "," TINUVIN 1130 "," ADEKA STAB LA-29 "manufactured by ADEKA," RUNA-93 "manufactured by Otsuka Chemical, etc. It is done.

  Examples of triazine organic compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis. (2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl)- Reaction product of 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl-glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl” And -6- (2,4-dibutoxyphenyl) -1,3-5-triazine.

  More specifically, “KEMISORB 102” manufactured by Chemipro Kasei Co., Ltd. “TINUVIN 400”, “TINUVIN 405”, “TINUVIN 460”, “TINUVIN 477-DW”, “TINUVIN 479”, “TINUVIN 1577” manufactured by BASF, Examples include “ADEKA STAB LA-46”, “ADEKA STAB LA-F70” manufactured by ADEKA, “CYASORB UV-1164” manufactured by Sun Chemical Co., Ltd., and the like.

  Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Examples include octoxybenzophenone and 2,2-di-hydroxy-4-methoxybenzophenone.

  More specifically, “KEMISORB 10”, “KEMISORB 11”, “KEMISORB 11S”, “KEMISORB 12”, “KEMISORB 111”, Sipro Kasei “SEESORB 101”, “SEESORB 107”, ADEKA manufactured by Chemipro Kasei Co., Ltd. “Adeka Stub 1413” manufactured by the company and the like can be mentioned.

<Solvent>
In the photosensitive coloring composition according to the embodiment of the present invention, the colorant (A) is sufficiently dispersed in a dye carrier such as an alkali-soluble resin (D) or a photopolymerizable compound (C), and a transparent glass substrate or the like is obtained. In order to make it easy to form a filter segment or a black matrix by applying a dry film thickness of 0.2 to 10 μm on the substrate, a solvent can be contained. Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-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-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, N-methylpyrrolidone, 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 monopropyl ether 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 Recall 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 Tons, methylcyclohexanol, acetate n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, and the like, used these alone or in mixtures.
The solvent can be used in an amount of 100 to 10000 parts by mass, preferably 500 to 5000 parts by mass with respect to 100 parts by mass of the colorant (A) in the photosensitive coloring composition.

<Other ingredients>
(Storage stabilizer)
The photosensitive coloring composition according to the embodiment of the present invention may contain a storage stabilizer. By containing a storage stabilizer, the viscosity with time of the composition can be stabilized. Examples of the storage stabilizer include 2,6-bis (1,1-dimethylethyl) -4-methylphenol, pentaerystyryl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl). Propionate], hindered phenols such as 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) 1,3,5-triazine, tetraethylphosphine, tri Organic phosphines such as phenylphosphine and tetraphenylphosphine, phosphites such as zinc dimethyldithiophosphate, zinc dipropyldithiophosphate and molybdenum dibutyldithiophosphate, sulfurs such as dodecyl sulfide and benzothiophene, benzyltrimethyl chloride, Quaternary ammonium chloride such as diethylhydroxyamine , Lactic acid, and organic acids and methyl ethers such as oxalic acid. May be used singly or as a mixture.

  A storage stabilizer is 0.01-20 mass parts with respect to 100 mass parts of coloring agents (A) in a coloring composition, Preferably it can be used in the quantity of 0.05-10 mass parts. By using 0.01 parts by mass or more of the storage stabilizer, the temporal stability of the photosensitive coloring composition is improved.

  Moreover, the photosensitive coloring composition by embodiment of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Production method of photosensitive coloring composition>
The photosensitive coloring composition according to the embodiment of the present invention comprises a three-roll mill, a two-roll mill, a sand mill, a kneader, an atom in a dye carrier such as a resin and / or a solvent, optionally with a colorant (A). A pigment dispersion is produced by finely dispersing using various dispersing means such as a lighter, and the photopolymerization initiator (B), alkali-soluble resin (D), photopolymerizable compound (C), Depending on the type, other photopolymerization initiators, sensitizers, polyfunctional thiols (H), antioxidants (F) polymerization inhibitors (G), UV absorbers, storage stabilizers, solvents, and other ingredients may be mixed and stirred. Can be manufactured. Moreover, the photosensitive coloring composition containing 2 or more types of pigments mixes each pigment dispersion separately finely in a pigment | dye carrier and / or a solvent, and also mixes a photoinitiator (B) or light. The polymerizable compound (C) and the like can be produced by mixing and stirring.

<Dispersing aid>
When dispersing the colorant (A) in the dye carrier, a dispersion aid such as a resin-type dispersant, a dye derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

[Resin dispersant]
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed 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-based dispersants such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resin, water-soluble polymer compound, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, used phosphoric acid ester and the like, they may be used alone or in combination, is not necessarily limited thereto.
Moreover, the resin-type dispersant may have an oxetane group. When the resin-type dispersant has an oxetane group, the colored composition containing the dispersant is excellent in heat resistance after being cured.

  The dispersant used in the present invention is preferably a polymer dispersant having a basic functional group, such as a nitrogen atom-containing graft copolymer, a tertiary amino group in the side chain, a quaternary ammonium base, or a nitrogen-containing heterocyclic ring. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by mass relative to the total amount of the colorant, and more preferably about 10 to 100% by mass from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemi Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS, BYKUMEN, etc., SOLPERSE-3000, 9000, 1300 manufactured by Nippon Lubrizol , 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, manufactured by BASF, etc. 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of Ajisupa -PA111, PB711, PB821, PB822, PB824, and the like are preferable.

Moreover, as a resin type dispersing agent used by this invention, it is also preferable to contain the following (S1) or (S2) as a resin type dispersing agent which has a carboxyl group.
(S1) A resin-type dispersant that is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride.
(S2) A polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. A resinous dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, JP2008-029901A, or JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that there are a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can obtain as a polymer (p1) which polymerized the ethylenically unsaturated monomer (r) containing. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride to form an ester bond, while the anhydride ring is opened, and the carboxylic acid Produce.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP2009-155406A, JP2010-185934A, JP2011-157416A, for example, a compound having a hydroxyl group By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. can get. In particular, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1).

  The difference between (S1) and (S2) is whether the polymer site obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and the like may be slightly different depending on various conditions, but theoretically the same can be obtained if the raw materials and reaction conditions are the same.

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

Examples of organic dyes include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, benzoids Indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, selenium pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. It is done.
Specific examples of the diketopyrrolopyrrole dye derivative include JP2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, JP2017-156397, phthalocyanine. JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, JP-A-575266, and anthraquinone-based dye derivatives include JP-A-63-264673, JP 09-272812 A, JP 10-245501 A, JP 10-265697 A, JP 2007-079094 A, WO 2009/025325 pamphlet, Kina Examples of the redone-based dye derivatives include JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, and examples of the dioxazine-based dye derivatives include JP-A-2011-162661 and thiazine indigo. JP-A-2007-314785 as a dye derivative, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-314621 as triazine dye derivatives. No. 168208, JP-A No. 2004-217842, JP-A No. 2007-314682, JP-A 2009-57478 as a benzoisoindole dye derivative, and JP-A No. 2003-167112 as a quinophthalone dye derivative. Publication, JP 2006-291194 A JP-A-2008-31281, JP-A-2012-226110, JP-A-2012-208329, JP-A-2014-5439 as naphthol dye derivatives, and JP-A-2001 as azo dye derivatives. No. 172520, JP 2012-172092 A, acidic substituents as JP 2004-307854, basic substituents as JP 2002-201377, JP 2003-171594, Known pigment derivatives described in JP-A-2005-181383, JP-A-2005-213404 and the like can be mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. However, the above organic dye residue has an acidic group, basic group, medium A compound having a substituent such as a functional group is synonymous with a pigment derivative.
These pigment derivatives can be used alone or in combination of two or more.

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

[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 may be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When adding a surfactant, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the added effect. When the content is more than 55 parts by mass, the dispersion may be affected by an excessive dispersant. .

  The photosensitive coloring composition according to the embodiment of the present invention can be prepared in the form of a solvent development type or alkali development type colored resist material. The colored resist material is a composition containing an alkali-soluble resin (D), a photopolymerizable compound (C), a photopolymerization initiator (B), and a solvent, and the colorant (A) is dispersed together with an optional dispersant. It has been made.

  The photosensitive coloring composition is obtained by means of centrifugal separation, sintering filter, membrane filter, or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

<Color filter>
Next, the color filter of the present invention will be described.
A color filter according to an embodiment of the present invention includes a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter includes at least one red filter. It may comprise a segment, at least one green filter segment, and at least one blue filter segment, or may comprise at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, a glass plate such as soda-lime glass, low alkali borosilicate glass, non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate can be used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography can be performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. 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.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove the uncured portion and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, a filter segment and a black matrix can be formed with higher accuracy than the printing method.

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.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

<Organic EL display device>
The organic EL display device in the present invention is a display device having a color filter formed of the red coloring composition for an organic EL display device of the present invention and a white light emitting organic EL element (hereinafter referred to as an organic EL element) as a light source. Preferably there is.

[Organic EL element (white light-emitting organic EL element)]
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. Further, thin films of inorganic semiconductors such as molybdenum oxide (abbreviation: MoO _x ), vanadium oxide (abbreviation: VO _x ), nickel oxide (abbreviation: NiO _x ), and inorganic insulation such as aluminum oxide (abbreviation: Al ₂ O ₃ ) An ultra-thin body film is also effective. In addition, 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (abbreviation: TDATA), 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N -Phenyl-amino] -triphenylamine (abbreviation: MTDATA), N, N'-bis (3-methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (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 MoO _x 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, 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 CaF ₂ , or an alkali metal oxide such as Li ₂ O 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 Alq ₃ 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 structure containing a red phosphor (JP-A-6-207170), a blue light emitting layer containing a blue fluorescent dye, and a green light emitting layer containing a red fluorescent dye. Have regions having include further structure of those that contain green phosphor (Japanese Patent Laid-Open No. 7-142169) or the like.

  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. In addition, metal complexes such as tris (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl) Can also be obtained from Further, a polymer such as poly (p-phenylene vinylene) may 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, SNO ₂ , 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 material. 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 deposition film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidification 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 element 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.

  EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In Examples and Comparative Examples, “parts” and “%” mean “parts by mass” and “% by mass”. PGMAc represents propylene glycol monomethyl ether acetate.

<Weight average molecular weight Mw>
The weight average molecular weight of the resin was measured in terms of polystyrene measured using HLC-8220GPC (manufactured by Tosoh Corporation) as a device, TSK-GEL SUPER HZM-N connected in series as a column, and THF as a solvent. It is a weight average molecular weight value.

<Acid value>
To 0.5 to 1 g of a resin solution or photopolymerizable compound, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly. An automatic titrator (“COM- 555 "manufactured by Hiranuma Sangyo Co., Ltd.) and the acid value (mgKOH / g) of the resin solution or photopolymerizable compound was measured. The acid value per solid content of the resin or photopolymerizable compound was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

<Particle size>
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). 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 primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

<Number of urethane bond groups>
The number of urethane groups in the photopolymerizable monomer is a measure of the number of urethane bonds contained in the molecule, and was calculated as follows.
<Number of urethane bonds in one molecule obtained by reaction of polyfunctional isocyanate> × <Ratio of polyfunctional acrylate produced by reaction in all photopolymerizable monomers> / <Average of photopolymerizable monomers Molecular weight>

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

<Manufacture of resin-type dispersant>
[Production Example 1]
(Resin type dispersant (P1) solution)
A reaction vessel equipped with a gas inlet tube, temperature, condenser and stirrer is charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of propylene glycol monomethyl ether acetate, and nitrogen gas Replaced with.
The reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution obtained by adding 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed that 95% had reacted by solid content measurement.
19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone and 0.4 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added at 100 ° C. The reaction was performed for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride had been half-esterified, the reaction was terminated, and propylene glycol monomethyl ether acetate was added and diluted so that the solid content would be 40% solids. A solution of a carboxylic acid resin dispersant (P1) having a value of 43 and a weight average molecular weight of 8,500 was obtained.

[Production Examples 2 to 6]
(Resin type dispersant (P2-6) solution)
The synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation amounts shown in Table 4 were used to obtain solutions of resin-type dispersants (P2) to (P6).

Abbreviations in Table 4 are shown below.
AIBN: 2,2′-azobisisobutyronitrile PGMAc: propylene glycol monomethyl ether acetate DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene

<Manufacture of colorants>
(Red treated pigment (A1))
Below, the specific synthesis | combining method of a red process pigment (A1) is shown with the reaction scheme (the following reaction scheme A). Other azo pigments according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo pigment is not limited to the following method.

(1) Synthesis of Compound (b) 90 parts of 2,3-hydroxynaphthoic acid and 1.2 parts of N, N-dimethylformamide were added to 573 parts of toluene, heated to 85 ° C., and 556.3 parts of thionyl chloride. Was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was refluxed for 1 hour. The above reaction solution was added dropwise over 30 minutes to a solution prepared by separately heating 80.9 parts of compound (a) and 264 parts of toluene at 85 ° C., and the mixture was refluxed for 2 hours. After cooling this reaction liquid to 95 ° C., 8.0 parts of 28% ammonia aqueous solution and 20 parts of water were added, and after stirring for 15 minutes at 95-100 ° C., toluene and unreacted compound (a) were removed by steam distillation. did. The precipitated reaction product was collected by filtration, washed with hot water, and then dried to obtain 152 parts (yield: 95.8%) of compound (b).

(2) Synthesis of azo pigment (A1b) After adding 36.3 parts of compound (c) to 252.2 parts of glacial acetic acid, 39.1 parts of 35% hydrochloric acid was added and cooled to -2 to 0 ° C. . After adding 42.2 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0-5 ° C. This reaction solution was added to a mixed solution consisting of 50.7 parts of the compound (b) prepared separately in the previous method, 67.1 parts of 25% sodium hydroxide solution, 772 parts of water, and 680 parts of isopropyl alcohol for 15 minutes. It was dripped at. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water and methanol, and dried to obtain 85.9 parts of azo dye 1. (Yield: 98%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment (A1b) shown in the above scheme A. The naphthol azo pigment (A1b) corresponds to the pigment represented by the general formula (1).

(3) Red processed pigment (A1)
Next, 80 parts of the azo pigment (A1b), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 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. 78 parts of red-treated pigment (A1) were obtained. The average primary particle size was 38 nm.

(Red processed pigment (A2))
Similar to the production of red treated pigment (A1) except that 66.8 parts of 3-aminobenztrifluoride were used instead of 80.9 parts of compound (a) used in the production of red treated pigment (A1). Thus, 80.0 parts (yield 98%) of an azo pigment (A2b) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment (A2b). The naphthol azo pigment (A2b) corresponds to the pigment represented by the general formula (1).

Naphthol azo pigment (A2b)

  Next, 80 parts of the azo pigment (A2b), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 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. 78 parts of red-treated pigment (A2) were obtained. The average primary particle size was 42 nm.

(Red processed pigment (A3))
The preparation of red processed pigment (A1) except that 24.9 parts of 3-amino-4-methoxybenzamide were used instead of 80.9 parts of compound (a) used in the preparation of red processed pigment (A1). The same operation was performed to obtain 80.0 parts (yield 97%) of an azo pigment (A3b). As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment (A3b). The naphthol azo pigment (A3b) corresponds to the pigment represented by the general formula (1).

  Next, 80 parts of the azo pigment (A3b), 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 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. 78 parts of red-treated pigment (A3) were obtained. The average primary particle size was 45 nm.

Naphthol azo pigment (A3b)

(Red processed pigment (A4))
Commercially available C.I. corresponding to the pigment represented by the general formula (1). I. 100 parts of Pigment Red 269 (PR269) (“Toner Magenta F8B” manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts of red process pigments (A4). The average primary particle size was 45 nm.

(Red processed pigment (A5))
Commercially available C.I. I. 100 parts of Pigment Red 177 (PR177) (“chromophthaled red A2B” 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) and kneaded at 60 ° C. for 6 hours. Then, salt milling was performed. The obtained kneaded product is poured into 3 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. 98 parts of red-treated pigment (A5) were obtained. The average primary particle size was 33 nm.

(Yellow treated pigment (A6))
C. I. 100 parts of Pigment Yellow 185 (PY185) (“Pariogen Yellow D1155” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. . The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A treated pigment (A6) was obtained. The average primary particle size was 45.7 nm.

(Yellow treated pigment (A7))
C. I. 100 parts of Pigment Yellow 138 (PY138) ("Pariotol Yellow K0960-HD" manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A treated pigment (A7) was obtained. The average primary particle size was 40.2 nm.

(Yellow treated pigment (A8))
C. I. 100 parts of Pigment Yellow 139 (PY139) (“Irgafore Yellow 2R-CF” manufactured by BASF), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. for 6 hours. Kneaded. The mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80 ° C. to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, dried at 80 ° C. overnight, and 95 parts of yellow A treated pigment (A8) was obtained. The average primary particle size was 43.2 nm.

(Yellow treated pigment (A9))
According to the synthesis method described in JP2012-226110A, a quinophthalone compound (b) represented by the chemical formula (10) was obtained.

Chemical formula (10) Quinophthalone compound (b)

  Subsequently, 100 parts of the obtained quinophthalone compound (b), 10 parts of the pigment derivative a of the chemical formula (11), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 60 ° C. for 8 hours. Next, the kneaded product is put into warm water, stirred for 1 hour while being heated to about 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of refined pigment (A9) were obtained. The average primary particle size was 40 nm.

Chemical formula (11) Dye derivative a

(Green treated pigment (A10))
Phthalocyanine green pigment C.I. I. 135 parts of Pigment Green 58 (“FAST OGEN GREEN A110” manufactured by DIC), 1500 parts of sodium chloride, and 330 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, this kneaded material is put into 6000 parts of water, stirred for 2 hours to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 85 ° C. overnight, pulverized, and 145 parts. Green-treated pigment (A10) was obtained.

(Green treated pigment (A11))
To a three-necked flask, 500 parts of 98% sulfuric acid, 50 parts of a phthalocyanine pigment represented by the formula (12), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred. The reaction was carried out at 0 ° C. for 6 hours. Thereafter, the reaction mixture was poured into 5000 parts of ice water at 3 ° C., and the precipitated solid was collected by filtration and washed with water. To a beaker, 500 parts of a 2.5% aqueous sodium hydroxide solution and the residue collected by filtration were added and stirred at 80 ° C. for 1 hour. Thereafter, this mixture was collected by filtration, washed with water, and dried to obtain a pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring.
Next, 500 parts of N-methylpyrrolidone, 50 parts of a pigment having an average of 10.1 bromine atoms substituted on the resulting phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-necked flask. The mixture was heated to 0 ° C. and reacted for 8 hours. After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain a green-treated pigment (A10) represented by the following formula (13). The average primary particle diameter of the obtained pigment was 30 nm.

Formula (12)

Formula (13)

(Blue treatment pigment (A12)
Phthalocyanine blue pigment C.I. I. 135 parts of Pigment Blue 15: 6 (“LIONOL BLUE E” manufactured by Toyocolor Co., Ltd.), 15 parts of pigment derivative b represented by the formula (14), 1500 parts of sodium chloride, and 330 parts of diethylene glycol, 1 gallon kneader made of stainless steel (Made by Inoue Seisakusho) and kneaded at 80 ° C. for 8 hours. Next, this kneaded material is put into 6000 parts of water, stirred for 2 hours to form a slurry, filtered, washed with water repeatedly to remove sodium chloride and diethylene glycol, dried at 85 ° C. overnight, pulverized, and 145 parts. A blue-treated pigment (A12) was obtained.

Chemical formula (14) Dye derivative b

(Salt-forming compound A13)
In the following procedure, C.I. I. A salt-forming compound (V) composed of Acid Red 52 and tristearyl monomethylammonium chloride which is a quaternary ammonium salt compound was prepared. C. so as to obtain a 10% aqueous solution. I. Acid Red 52 is dissolved in water and heated to 30 to 50 ° C., then tristearyl monomethyl ammonium chloride is dissolved in a methanol / water = 20/80 solution so as to form a 5% solution, and the solution is added dropwise little by little. After dropwise addition of tristearyl monomethylammonium chloride, the mixture is stirred for 3 hours at 30 to 50 ° C. and sufficiently reacted. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound of acid red 52 and tristearyl monomethylammonium chloride, a salt-forming compound (A13) was obtained.

<Manufacture of alkali-soluble resin (D) solution>
[Alkali-soluble resin D1]
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAc) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C. while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile is used as a catalyst required for the reaction of the precursor at this stage. The polymerization reaction was carried out dropwise over 2.5 hours.
Next, the inside of the flask was purged with air, and 29 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, and the mixture was heated at 120 ° C. for 5 hours. Reaction was performed and the resin solution whose weight average molecular weight (Mw) is about 10,500 was obtained. Since the added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, no carboxyl group is generated in the resin structure.
Furthermore, as a catalyst required for reaction of 46 parts of tetrahydrophthalic anhydride and the precursor at this stage, 0.5 part of triethylamine was added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.
PGMAc was added so that the nonvolatile content was 20% by mass to obtain an alkali-soluble resin D1 solution. The weight average molecular weight (Mw) was 11,500, and the acid value was 103 mgKOH / g.

[Alkali-soluble resin D2]
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% by mass. Thus, an alkali-soluble resin D2 solution was obtained. The weight average molecular weight (Mw) was 26,000.

<Production of photopolymerizable compound (C)>
(Photopolymerizable compound (C1))
In a 1 L four-necked flask, 582 g of hexa / penta mixed acrylate of dipentaerythritol, 36 g of hexamethylene diisocyanate and 0.5 g of N, N-dimethylbenzylamine are charged and reacted at a temperature of 50 to 70 ° C. for 8 hours. The disappearance of isocyanate absorption was confirmed by IR analysis.
In addition, 24 g of mercaptopropionic acid and 0.6 g of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours to obtain a product containing a polyfunctional acrylate having a urethane bond and a carboxyl group. In the product, the proportion of the polyfunctional acrylate was 45% by mass, and a photopolymerizable compound (C1) in which the remainder was occupied by another photopolymerizable monomer was obtained.
The acid value of this photopolymerizable compound (C1) was 28 mgKOH / g, and the content of the carboxyl group-containing polyfunctional monomer was 40% in terms of area by gel permeation chromatography. The number of urethane groups of the photopolymerizable compound (C1) was 0.99 × 10 ⁻³ mol / g, and the number of double bond groups was 8.08 × 10 ⁻³ mol / g.

(Photopolymerizable compound (C2))
A product containing polyfunctional acrylate having urethane bond, charged with 623g of dipentaerythritol hexa / penta mixed acrylate and 44g of hexamethylene diisocyanate in a five-neck reaction vessel with an internal volume of 1 liter and reacted at 60 ° C for 8 hours. Got. The proportion of the polyfunctional acrylate in the product was 45% by mass, and a photopolymerizable compound (C2) in which the remainder was occupied by another photopolymerizable monomer was obtained.
In addition, it was confirmed by IR analysis that no isocyanate group was present in the reaction product. The number of urethane groups of the photopolymerizable compound (C2) was 1.04 × 10 ⁻³ mol / g, and the number of double bond groups was 9.01 × 10 ⁻³ mol / g.

<Manufacture of colorant dispersion>
[Pigment dispersion (P-R1)]
After uniformly stirring and mixing the mixture having the following composition, it was dispersed for 5 hours with an Eiger mill (Eiger Japan's “Mini Model M-250 MKII”) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion P-R1 was prepared.
Red treated pigment (A1): 15.00 parts Resin-type dispersant (P-1) solution: 2.87 parts Alkali-soluble resin D1 solution: 19.28 parts Propylene glycol monomethyl ether acetate: 62.86 parts

[Pigment dispersion (P-R2-5, P-Y1-4, P-G1-2, P-B1)]
The pigment dispersions (P-R2-5, P-Y1-Y4, and P-R2-5 are the same as the pigment dispersion (PR-1) except that the treated pigment and resin-type dispersant solution are changed to the types shown in Table 5. P-G1-2 and P-B1) were prepared.

[Salt-forming compound-containing resin solution (P-V1)]
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a salt-forming compound-containing resin solution (P-V1).
Salt-forming compound (A13): 6.0 parts Alkali-soluble resin D1 solution: 60.0 parts Cyclohexanone: 10.0 parts Propylene glycol monomethyl ether acetate: 24.0 parts

[Pigment dispersion P-Bk]
A black pigment dispersion P-Bk was prepared in the same manner as the pigment dispersion using a mixture having the following composition.
Carbon black (“MA77” manufactured by Mitsubishi Chemical Corporation): 14.00 parts Resin-type pigment dispersant: 4.78 parts (“Solsperse 20000” manufactured by Nippon Lubrizol)
Alkali-soluble resin D1 solution: 6.13 parts Cyclohexanone: 75.10 parts

<Preparation of photosensitive coloring composition for organic EL display device>
[Examples 1 to 35 and Comparative Examples 1 to 5]
(RR-1 to 36, RG-1 to 2, RB-1, RBk-1)
Each material was mixed and stirred at a formulation ratio shown in Table 6-9, and filtered through a 1 μm filter to obtain a photosensitive colored composition of each color.

Abbreviations in Table 6-9 are shown below.
Photopolymerization initiator B1: Oxime ester-based initiator formula (3) represented by the following formula (3)

Photopolymerization initiator B2: Oxime ester-based initiator formula (4) represented by the following formula (4)

Photopolymerization initiator B3 (oxime ester type): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime) ) ("Irgacure OXE02" manufactured by BASF)

Photopolymerization initiator B4 (acetophenone series): 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (“Irgacure 369E” manufactured by BASF)
Photopolymerization initiator B5 (phosphine series): 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (“Irgacure TPO” manufactured by BASF)

Photopolymerizable compound C1: Product containing a polyfunctional acrylate having a urethane bond and a carboxyl group produced in the above production example. Photopolymerizable compound C2: A polyfunctional acrylate having a urethane bond produced in the above production example. Containing product / photopolymerizable compound C3: acrylate of ε-caprolactone modified dipentaerythritol (“KAYARAD DPCA-60” manufactured by Nippon Kayaku Co., Ltd.)
Photopolymerizable compound C4: acrylate of ε-caprolactone-modified dipentaerythritol (“KAYARAD DPCA-120” manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerizable compound C5: Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)

Silane coupling agent E1 (containing reactive unsaturated double bond): 3-methacryloxypropyltriethoxysilane (“KBE-503” manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent E2 (containing reactive unsaturated double bond): 3-acryloxypropyltrimethoxysilane (“KBM-5103” manufactured by Shin-Etsu Chemical Co., Ltd.)
Silane coupling agent E3 (containing epoxy group): 3-glycidoxypropylmethyldimethoxysilane (“Z-6044” manufactured by Toray Dow Corning)

Antioxidant F1 (hindered phenol type): 2 pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“IRGANOX1010” manufactured by BASF)
Antioxidant F2 (hindered phenol type): 1,3,5-tris (3,5-ditertiary butyl 1-4 hydroxybenzyl) -1,3,5 triazine-2,4,6 (1H, 3H , 5H) Trion (Adeka AO-20)
Antioxidant F3 (benzotriazole type): 2,4′-methylenebis [6- (2H-benzotriazole-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol] (ADEKA ADK STAB LA-31RG made by the company)

Polymerization inhibitor G1: Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)

Polyfunctional thiol H1: pentaerythritol tetrakis (3-mercaptopropionate) (“PEMP” manufactured by Sakai Chemical Industry Co., Ltd.)

・ Organic solvent: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive coloring composition for organic EL display device>
The obtained photosensitive coloring composition was evaluated by the following methods. The results are shown in Table 10.

[Filter segment and black matrix pattern formation]
The obtained photosensitive coloring composition was applied to a 10 cm × 10 cm glass substrate by a spin coating method, then heated in a clean oven at 70 ° C. for 15 minutes to remove the solvent, and after drying, the film thickness was 1.6. A five-level coating film of /1.8/2.0/2.2/2.5 μm was obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a 25 ° C. aqueous potassium hydroxide solution, washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 30 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time.
The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]
The film thickness of the filter segment formed at a film thickness of 2.0 μm by the above method or the pattern film thickness at the 100 μm photomask portion of the black matrix was measured, and the minimum exposure amount that was 90% or more with respect to the film thickness after coating was evaluated. . The smaller the minimum exposure, the higher the sensitivity and the better the photosensitive coloring composition. The rank of evaluation is as follows.
◎: less than ^{30mJ / cm 2 ○: 30mJ /} cm 2 or more and less than ^{50mJ / cm 2 △: 50mJ /} cm 2 or more, 100mJ / cm ² less than ×: 100mJ / cm ² or more

[Linearity evaluation]
Evaluation was performed by observing the pattern in the 100 μm photomask portion of the filter segment or black matrix formed with a film thickness of 2.0 μm by the above method using an optical microscope. The rank of evaluation is as follows.
◎: Good linearity ○: Slightly no linearity △: Partially poor linearity ×: Poor linearity

[Pattern shape evaluation]
The cross section of the pattern in the 100 μm photomask portion of the filter segment or black matrix formed by the above method and evaluated in five levels was observed and evaluated using an electron microscope. The pattern cross section has a good forward taper and can maintain a shape with various film thicknesses. The rank of evaluation is as follows.
◎: Forward tapered shape with a gentle cross section at all 5 levels ○: A forward tapered shape with a gentle cross section at 3 to 4 levels △: A forward tapered shape with a smooth cross section at the 1 to 2 levels ×: Reverse tapered shape at all levels shape

[Resolution evaluation (resolution)]
The pattern in the 25 μm photomask portion of the 2.5 μm filter segment or black matrix formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The rank of evaluation is as follows.
◎: Good with no connection or chipping with adjacent pattern 〇: Slight connection or chipping with adjacent pattern is observed △: Many connections or chipping with adjacent pattern are observed ×: All patterns are connected, or All patterns are peeled off

[Development resistance evaluation]
During spray development, the pattern film thickness is measured at a 2.0 μm filter segment or black matrix 100 μm photomask that is developed and developed in twice the appropriate time, and developed with the appropriate development time. The film thickness was compared. The rank of evaluation is as follows.
A: Film thickness difference within 5% B: Film thickness difference within 5-20% B: Film thickness difference greater than 20% and within 40%
X: The film thickness difference is larger than 40%. Or chipping or peeling occurs

[Evaluation of chemical resistance]
The 2.0 μm filter segment or black matrix formed by the above method is immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and the pattern on the 100 μm photomask portion is observed using an optical microscope. And evaluated. The rank of evaluation is as follows.
◎: Appearance and color are good without change ○: Some wrinkles are generated, but color is good without change △: Wrinkles are generated, color is slightly changed ×: Peeling or discoloration occurs

  As shown in Table 4, the filter segment and the black matrix formed using the photosensitive coloring composition of Examples 1 to 35 in Examples 1 to 35 have good sensitivity, linearity, and resolution, and finished film thickness. The pattern shape margin was wide.

  According to the configuration of the present application, an appropriate amount of the silane coupling agent (E) controls the adhesion between the coating film and the substrate and the development solubility without generating a residue during development, and the photopolymerizable compound (C The urethane bond group and / or caprolactone-modified group in FIG. 2 can provide sufficient flexibility to the coating film in the shape before post-baking, thereby generating a heat flow by thermal crosslinking such as post-baking. It is inferred to have a thick margin.

<Example of manufacturing 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 1 (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 150 nm was obtained. On the hole injection layer, the compound (R-2) and the compound (R-3) shown in Table 3 are further co-evaporated at a composition ratio of 100: 2 to form a first light emitting layer having a thickness of 10 nm. did. Furthermore, the compound (B-1) and the compound (B-4) in Table 1 were co-evaporated at a composition ratio of 100: 3 to form a second light emitting layer having a thickness of 20 nm. On this light emitting layer, 5 nm of α-NPD and 20 nm of the compound (G-3) in Table 2 were further evaporated to form a third light emitting layer. Further, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form an electron injection layer having a film thickness of 35 nm, and then an electrode was formed by first depositing 1 nm of lithium fluoride and then 200 nm of aluminum. The organic EL element 1 was obtained.

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 950 (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 11 shows the ratio (I2 / I1) of the emission intensity I2.

<Production of color filter>
A black matrix is patterned on a glass substrate, and the red photosensitive coloring composition (RR-7) of the present invention is applied on the substrate with a spin coater in the organic EL element (EL-1) light source (hereinafter referred to as green, It was applied so that x = 0.655 and y = 0.325. The film was irradiated with ultraviolet rays of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask.
Next, spray development was performed with an alkaline developer composed of 0.05% by weight potassium hydroxide aqueous solution to remove unexposed portions, and then the substrate was washed with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter. A segment was formed. In the same manner, the blue photosensitive coloring composition of the present invention (RG-1) was adjusted so that x = 0.291 and y = 0.600. 2), a green filter segment and a blue filter segment were formed so that x = 0.141 and y = 0.084, and a color filter was obtained.

By using the photosensitive coloring composition of the present invention, a high-quality color filter could be produced. Moreover, when the organic EL display element was produced combining the obtained color filter and organic EL element (EL-1), the favorable color characteristic was acquired.

Claims (10)

Photosensitive for organic EL display device comprising a colorant (A), a photopolymerization initiator (B), a photopolymerizable compound (C), an alkali-soluble resin (D), and a silane coupling agent (E). In the total coloring matter in the photosensitive coloring composition, the coloring agent (A) is 42 to 60% by mass, the photopolymerizable compound (C) is 15 to 35% by mass, and the silane coupling agent (E 0.1 to 10% by mass, and the photopolymerizable compound (C) has at least one bond selected from the group consisting of a urethane bond and a bond derived from caprolactone modification in the molecule. Photosensitive coloring composition for organic EL display devices. The photosensitive coloring composition for organic EL display devices according to claim 1, wherein the silane coupling agent (E) has an unsaturated double bond. The photosensitive coloring composition for organic EL display devices according to claim 1 or 2, further comprising an antioxidant (F) and / or a polymerization inhibitor (G). The photosensitive coloring composition for organic EL display devices of Claim 3 in which antioxidant (F) contains a hindered phenol type compound. 5. The organic EL display device according to claim 1, wherein the colorant (A) contains a red pigment and a yellow pigment, and the red pigment contains a pigment represented by the following general formula (1). Photosensitive coloring composition.
General formula (1)

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR represents a ¹² or _SO 2 ^{NHR 13.} R ^{7 to} R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The colorant (A) is C.I. I. The photosensitive coloring composition for organic electroluminescent display devices of any one of Claims 1-5 containing Pigment Red 269. The photosensitive coloring composition for organic EL display devices according to any one of claims 1 to 6, wherein the photopolymerization initiator (B) contains a compound represented by the following general formula (2).
General formula (2)

[In General Formula (2), R _{1 to} R ₄ each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, substituted or Unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl Represents a group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. ] The photosensitive coloring composition for organic EL display devices according to claim 7, wherein the compound represented by the general formula (2) is a compound represented by the following formula (3) or the following formula (4).
Formula (3)

Formula (4)

A color filter provided with the filter segment formed from the photosensitive coloring composition for organic EL display devices in any one of Claims 1-8 on a transparent substrate. An organic EL display device comprising the color filter according to claim 9 and a white organic EL light source.