JP7353550B1 - Photosensitive coloring compositions, color filters, image display devices, and solid-state imaging devices - Google Patents

Abstract

An object of the present invention is to provide a photosensitive coloring composition that leaves little residue in a developing process and is compatible with heat resistance. [Solution] A photosensitive coloring composition containing a colorant (A), a dispersion resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D), wherein the dispersion resin (B) is , a photosensitive coloring composition comprising a resin (B1) having one or more of epoxy groups and oxetanyl groups, and a photopolymerizable compound (C) comprising a ring structure-containing polyfunctional polyester acrylate. [Selection diagram] Figure 1

Description

The present invention relates to a photosensitive coloring composition used for manufacturing color filters used in liquid crystal display devices, solid-state image sensors, and the like.

Generally, in a liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film is further formed on the transparent electrode for aligning the liquid crystal in a certain direction. . In order to obtain the performance of these transparent electrodes and alignment films, high-temperature treatment (post-baking) at 200°C or higher, preferably 230°C or higher is generally required in the manufacturing process for forming color filters (also called pixels). .

However, if heat treatment is performed at a higher temperature (e.g., 300°C or higher) after the high-temperature treatment (post-bake), the shrinkage rate of the pixel film increases, and other films (e.g., inorganic film) formed on the pixel increase. ) may cause problems such as cracks occurring. Therefore, Patent Document 1 discloses a photosensitive coloring composition containing polyimide or a polyimide precursor instead of the conventional acrylic resin.

International Publication No. 2021/020360

However, although conventional photosensitive coloring compositions have improved heat resistance, they have a problem of low solubility in developing solutions and the formation of residues during the development process.

An object of the present invention is to provide a photosensitive coloring composition that leaves little residue during the development process and is compatible with heat resistance.

In the photosensitive coloring composition of the present invention, when the photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate and has a thermosetting compound (E), the thermosetting compound (E) is When the dispersion resin (B) is a compound having one or more selected from epoxy groups, oxetanyl groups, blocked isocyanate groups, and tert-butyl groups, and does not have a thermosetting compound (E), the dispersion resin (B) is an epoxy group, an oxetanyl It is characterized by being a resin having one or more selected from group, blocked isocyanate group, and tert-butyl group.

According to the present invention described above, it is possible to provide a photosensitive coloring composition that leaves little residue in the development step and is compatible with heat resistance. Further, the present invention can also provide a color filter, a liquid crystal display device, and a solid-state image sensor.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device including a color filter.

Define terms used herein. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, each , "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate" or "acrylamide and/or methacrylamide". "C.I." mentioned herein means color index (C.I.). Colorants include pigments and dyes.

A first aspect of the photosensitive coloring composition of the present invention includes a colorant (A), a dispersion resin (B), a photopolymerizable compound (C), and a photopolymerization initiator (D). contains a resin (B1) having one or more selected from oxetanyl groups, blocked isocyanate groups, and tert-butyl groups, and the photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate.

The second aspect of the photosensitive coloring composition of the present invention comprises a colorant (A), a dispersion resin (B) or a binder resin, a photopolymerizable compound (C), a photoinitiator (D), and a thermosetting compound. (E), the photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate, and the thermosetting compound (E) contains an epoxy group and an oxetanyl group. A compound having one or more of these (excluding dispersion resin (B)).

The third aspect of the photosensitive coloring composition of the present invention comprises a colorant (A), a dispersion resin (B) or a binder resin, a photopolymerizable compound (C), a photopolymerization initiator (D), and a thermosetting compound. (E), the dispersion resin (B) contains a resin (B1) having one or more selected from oxetanyl group, blocked isocyanate group, and tert-butyl group, and the thermosetting compound (E) contains epoxy The photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate.

These photosensitive coloring compositions are preferably applied onto a base material (also referred to as a substrate) to form a film, and the film can be patterned by photolithography. Preferably, the pattern is used as pixels of a color filter.

The reason why the first aspect of the photosensitive coloring composition of the present invention can solve the above problems is speculated below.
When a color filter (CF) is produced using a photosensitive coloring composition, one or more thermosetting groups selected from an oxetanyl group, a blocked isocyanate group, and a tert-butyl group in the resin (B1) undergo post-baking. The strength of the CF film increases as it is thermally cured during the process. As a result, high heat resistance (small spectral changes, small shrinkage rate of the film, and less cracking) can be obtained even when exposed to a high temperature state of 300° C., for example. In addition, when a hydrocarbon ring-containing polyfunctional polyester acrylate is contained in an appropriate amount, it has an ester bonding moiety consisting of a polyhydric alcohol and a polybasic acid, which improves the affinity with the developer and further suppresses residue after development. .

<Colorant (A)>
The colorant (A) contains a pigment or dye. The pigment is preferably an organic or inorganic pigment. The pigment is preferably a pigment with high color development and high heat resistance, particularly a pigment with high heat decomposition resistance, and usually an organic pigment is used. Preferred organic pigments are shown below using color index numbers.

The red pigment is, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP2014-134712A, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, a pigment described in JP 2014-134712, a pigment described in Patent No. 6368844, More preferably C. I. Pigment Red 177, 254, 291, 295, 296, the pigment described in Japanese Patent Application Publication No. 2014-134712, and the pigment described in Patent No. 6368844.

The orange pigment is C. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and the like.

Blue pigments include, for example, 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 heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, more preferably C.I. I. Pigment Blue 15:6.

The purple pigment is, for example, 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, etc. Among these, from the viewpoint of heat resistance, light resistance, and transmittance of the filter segment, C.I. I. Pigment Violet 19 or 23, more preferably C.I. I. Pigment Violet 23.

Green pigments include, for example, C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, pigments described in JP 2017-111398A, and the like. Among these, from the viewpoint of transmittance, C.I. I. Pigment Green 36, 58, 59, 62, 63, which are pigments described in JP 2017-111398A.

Yellow pigments include, for example, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, pigments described in JP 2012-226110A, and the like. Preferably C. I. Pigment Yellow 138, 139, 150, 185, 231, 233, which are pigments described in JP 2012-226110A.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, amber, synthetic iron. Examples include black. Inorganic pigments are used in combination with organic pigments in order to balance saturation and brightness while ensuring good coating properties, sensitivity, developability, etc.

<Refining of organic pigments>
When using an organic pigment, it is preferable to perform a fine treatment and then mix it with other raw materials. Examples of the method for the micronization treatment include wet grinding, dry grinding, and solution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm.

Resin can be added as needed during the salt milling process. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of resin used is preferably 50 to 200 parts by weight per 100 parts by weight of the pigment.

<Removal of metal>
If a large amount of a specific metal element is present in the photosensitive coloring composition as an impurity other than the constituent components of the pigment, dispersion stability over time may decrease, heat resistance may decrease, or sensitivity may decrease. Furthermore, color filters containing specific metal elements may generate foreign matter, which tends to cause a decrease in brightness. In order to avoid these problems, the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is set to 500 mass ppm. It is preferable to suppress it to below.

The total amount of the specific metal element is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. Further, the lower limit of the total amount of the specific metal element is not particularly limited, but is preferably 1 ppm or more by mass, and more preferably 5 ppm or more by mass. Within the above range, it is possible to obtain a photosensitive coloring composition that can reduce costs, has excellent storage stability, and can form a color filter with less generation of foreign matter and less reduction in brightness.

The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, and more preferably 50 mass ppm or less.

In addition, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that make up pigments should be suppressed as much as possible, so impurities that do not make up pigments should be suppressed as much as possible. can be removed. Furthermore, since Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (eg, catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, they are removed as much as possible.

Methods for removing metals mixed in from the colorant (A) or its production equipment include JP-A No. 2010-83997, JP-A No. 2018-36521, JP-A No. 7-198928, and JP-A No. 8-333521. Examples include a method of washing with water as disclosed in Japanese Patent Publication No. 2009-7432, and a method of removing magnetic foreign matter using a magnet as described in Japanese Patent Application Publication No. 2011-48736. A single method or a combination of these methods may be used as appropriate.

The content of the specific metal element can be measured by inductively coupled plasma emission spectroscopy (ICP).

<Dye>
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are dye derivatives and lake pigments obtained by turning dyes into lakes.

In addition, dyes include acid dyes having acidic groups such as sulfonic acid and carboxylic acid, inorganic salts of acid dyes; acid dyes and quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. salt-forming compounds; salt-forming compounds such as resin components having these amino groups and acidic dyes; and the like. A salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent fastness. Note that the compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types and compatibility with pigments.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, Quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

<Dye derivative>
The photosensitive coloring composition can use a dye derivative as necessary. A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, or phosphoric acid groups, as well as amine salts thereof, sulfonamide groups, or basic substituents such as tertiary amino groups at the terminals. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, diketopyrrolopyrrole dye derivatives include JP-A No. 2001-220520, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, JP 2017-156397 pamphlet, and phthalocyanine-based dye derivatives. Pigment derivatives are disclosed in JP-A No. 2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, and Patent No. 5753266. Anthraquinone-based pigment derivatives are described in JP-A-63-264674 and JP-A-09-09. -272812, JP 10-245501, JP 10-265697, JP 2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP 48-54128, JP-A-03-9961, JP-A 2000-273383, dioxazine dye derivatives, JP-A 2011-162662, thiazine indigo dye derivatives, JP-A 2007-314785, triazine dye derivatives are JP-A-61-246261, JP-A-11-199796, JP-A 2003-165922, JP-A 2003-168208, JP-A 2004-217842, and JP-A 2007-314681. , benzisoindole dye derivatives are disclosed in JP-A No. 2009-57478, and quinophthalone-based dye derivatives are described in JP-A Nos. 2003-167112, 2006-291194, 2008-31281, and 2012. -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic The substituent is described in JP-A No. 2004-307854, and the basic substituent is described in JP-A-2002-201377, JP-A 2003-171594, JP-A 2005-181383, and JP-A 2005-213404. Mention may be made of the dye derivatives described. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

The dye derivatives can be used alone or in combination of two or more types.

The amount of the dye derivative used is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, based on 100 parts by weight of the organic pigment.

By adding a pigment derivative to an organic pigment and performing micronization treatments such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed to the surface of the organic pigment and no pigment derivative is added. The primary particles of the organic pigment can be made finer than in the case of the conventional method.

<Dispersion resin (B)>
The dispersion resin (B) is a resin having an acidic group or a basic group and capable of dispersing the colorant (A).
In the first aspect of the photosensitive coloring composition of the present invention, the dispersion resin (B) is a dispersion resin having one or more types selected from thermally crosslinkable groups, such as an oxetanyl group, a blocked isocyanate group, and a tert-butyl group. (B1) included. The dispersion resin (B1) has a molecular structure that has a vinyl polymer part of the graft chain which is a steric repulsion part and an aromatic ring and a carboxyl group directly bonded to the aromatic ring in the pigment adsorption part to improve dispersibility and heat resistance. preferable. Furthermore, it is preferable that the vinyl polymer portion contains a (meth)acryloyl group. This provides photocrosslinkability.

The dispersion resin (B1) is, for example, a resin described in JP-A No. 2009-155406.

The dispersion resin (B1) has one or more thermally crosslinkable groups selected from oxetanyl group, blocked isocyanate group, and tert-butyl group in the vinyl polymer site. This further improves heat resistance.

Examples of the ethylenically unsaturated monomer (e) having a blocked isocyanate group include Karenz MOI-BM and Karenz MOI-BP (manufactured by Showa Denko K.K.).

Examples of the ethylenically unsaturated monomer (f) having an oxetane group include ETERNACOLL OXMA (manufactured by Ube Industries, Ltd.).

Examples of the ethylenically unsaturated monomer (g) having a tert-butyl group include tert-butyl methacrylate and tert-butyl acrylate.

The aromatic ring and the pigment adsorption site having a carboxyl group directly bonded to the aromatic ring are derived from one or more acid anhydrides selected from, for example, tetracarboxylic anhydride or tricarboxylic anhydride.

The acid value of the dispersion resin (B1) is preferably 10 to 250 mgKOH/g, and 40 to 200 mgKOH/g.
gKOH/g is more preferred, and 50 to 160 mgKOH/g is even more preferred. Appropriate acid value improves storage stability.

The Tg of the vinyl polymer moiety of the dispersion resin (B1) is preferably -50°C or higher, more preferably -30°C or higher, and even more preferably -10°C or higher. When the glass transition temperature is −10° C. or higher, the cross-sectional shape of the color filter pattern after development is greatly improved, so that a fine pixel pattern with better precision can be formed. Note that the upper limit of Tg is preferably 100°C.

The weight average molecular weight of the vinyl polymer portion of the dispersion resin (B1) is preferably from 500 to 30,000, more preferably from 5,000 to 20,000, even more preferably from 7,000 to 10,000.

The number average molecular weight of the vinyl polymer portion of the dispersion resin (B1) is preferably 2,000 to 6,000.

The dispersion resin (B) can be classified into comb-shaped dispersion resins and linear dispersion resins when classified by molecular structure. Among these, comb-shaped dispersion resins are preferred.

The comb-shaped dispersion resin can be synthesized, for example, by adding a hydroxyl group in a vinyl polymer having two hydroxyl groups at one end to a tetracarboxylic acid anhydride. The tetracarboxylic acid anhydride that is the raw material for the comb-shaped dispersion resin and the raw material for the vinyl polymer that is part of the structure are described in, for example, WO2008/007776.

The tetracarboxylic anhydride may have any structure as long as it has two carboxylic anhydride groups. The tetracarboxylic anhydride is preferably an aromatic tetracarboxylic dianhydride from the viewpoint of making the photosensitive coloring composition low in viscosity. Aromatic tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, ethylene glycol dianhydride trimellitic acid ester, 3,3' , 4,4'-biphenyl ether tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dioic anhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic acid Preferred are dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. Among these, pyromellitic anhydride is more preferred. Tetracarboxylic acid anhydrides can be used alone or in combination of two or more.

For example, a linear dispersion resin having a carboxyl group can be synthesized by adding a hydroxyl group in a vinyl polymer having two hydroxyl groups at one end to a tricarboxylic acid anhydride. Examples include compounds described in JP-A No. 2011-157416, JP-A No. 2009-251481, JP-A No. 2007-23195, and JP-A No. 1996-143651.

Examples of tricarboxylic anhydrides include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic acid Anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride ), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'- Examples include biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, trimellitic anhydride is more preferred.

The dispersion resin (B) is a resin that has an adsorption group that has a high affinity for the colorant (A) and a relaxation site that has an affinity for components other than the colorant (A). The dispersion resin (B) is, for example, WO 2008/007776, JP 2008-029901, JP 2010-18934, JP 2011-157416, JP 2009-251481, JP 2007- It is described in JP-A No. 23195, JP-A No. 1996-143651, JP-A No. 2007-140487, and the like. Dispersion resins (B) other than those mentioned above include urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and ammonium salts of polycarboxylic acids. , polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic esters, modified products thereof, poly(lower alkylene imine) and polyesters having free carboxyl groups. Oil-based dispersants such as formed amides and their salts, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyester-based , a modified polyacrylate type, an ethylene oxide/propylene oxide addition compound, a phosphoric acid ester type, and the like. These can be used alone or in combination of two or more.

Preferred examples of the dispersion resin having a basic functional group include a nitrogen atom-containing graft copolymer, a nitrogen atom-containing graft copolymer, and a nitrogen atom-containing graft copolymer having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle, etc. in the side chain. Examples include acrylic block copolymers and urethane polymer dispersants.

Furthermore, as disclosed in JP-A No. 2009-185277, a dispersion resin having an aromatic carboxyl group,

The content of the dispersion resin (B) is preferably 5 to 25% by mass, more preferably 10 to 20% by mass, based on the nonvolatile components of the photosensitive coloring composition.

Resin (B1) having one or more types selected from oxetanyl group, blocked isocyanate group, and tert-butyl group and thermosetting compound ( The total content with E) is preferably 50 to 100% by mass, more preferably 65 to 100% by mass.

<Photopolymerizable compound (C)>
The photopolymerizable compound (C) is a monomer or oligomer having a polymerizable unsaturated group. The polymerizable unsaturated group is an ethylenically unsaturated group such as a vinyl group, (meth)acryloyl group, or allyl group. The number of the polymerizable unsaturated groups is preferably 2 or more, more preferably 3 or more. Further, the number of the polymerizable unsaturated groups is preferably 20 or less.

The photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate. The number of polymerizable unsaturated groups in the ring structure-containing polyfunctional polyester acrylate is preferably 3 or more.

Since the photopolymerizable compound (C) contains a hydrocarbon ring-containing polyfunctional polyester acrylate, when a color filter is produced using the photosensitive coloring composition of the present invention, it does not react even when exposed to a high temperature state of, for example, 300°C. High heat resistance (small spectral changes, low film shrinkage, less likely to cause cracks). Furthermore, it is preferable to contain a hydrocarbon ring-containing polyfunctional polyester acrylate in an appropriate amount. Since the hydrocarbon ring-containing polyfunctional polyester acrylate has an ester bonding moiety made of a polyhydric alcohol and a polybasic acid, its affinity with a developing solution is improved, thereby making it possible to further suppress residues after development.
The hydrocarbon ring-containing polyfunctional polyester acrylate is preferably a compound represented by general formula (1) or a compound having a bisphenol A skeleton, and more preferably a compound represented by general formula (1). The compound represented by general formula (1) is preferably a compound containing a structural unit derived from an isocyanurate ring or a compound containing a structural unit derived from bisphenol A. This further improves heat resistance. The compound represented by the general formula (1) is preferably a compound having an ester bond, which is a reaction product of a polyhydric alcohol (X) and a polybasic acid (Y) having a cyclic structure.

General formula (1)

The symbols in general formula (1) are as follows.

The compound of general formula (1) is shown below. However, it is not limited to these.

Commercial products of the compound represented by general formula (1), a ring structure-containing polyfunctional polyester acrylate which is a compound having a bisphenol A skeleton, are Aronix M-7100, 7300K, 8030, 8060, 8100, 8530, and 8560 manufactured by Toagosei Co., Ltd. , 9050, etc.

The photopolymerizable compound (C) can contain photopolymerizable monomers other than the hydrocarbon ring-containing polyfunctional polyester acrylate. Other photopolymerizable monomers include acid group-containing monomers, urethane bond-containing monomers, and other monomers.
(Acid group-containing monomer)
Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Acid group-containing monomers include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; ) Examples include esterified products with acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

(Urethane bond-containing monomer)
The urethane bond-containing monomer is, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with an alcohol, and then a (meth)acrylate having a hydroxyl group. Examples include polyfunctional urethane acrylates obtained by reaction.

(Meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. ) 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, a reaction product of an epoxy group-containing compound and carboxy(meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

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

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, ) 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, phenoxy Tetraethylene 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 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, methylol Various acrylic esters and methacrylic esters such as (meth)acrylic acid ester of melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta Examples include erythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

The content of the hydrocarbon ring-containing polyfunctional polyester acrylate is preferably 25 to 75% by mass, more preferably 30 to 70% by mass based on 100% by mass of the photopolymerizable compound (C). When blended in an appropriate amount, curability and developability are further improved.

The content of the photopolymerizable compound (C) is preferably 5 to 40% by mass, more preferably 10 to 35% by mass, based on the nonvolatile components of the photosensitive coloring composition.

<Binder resin>
The binder resin is a resin that has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when forming a film with a thickness of 2 μm. Note that the transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, thermoplastic resin, active energy ray curable resin, and the like. The active energy ray-curable resin is a thermoplastic resin with a polymerizable unsaturated group added thereto. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkaline development step during color filter production, and an acidic group is required.

Binder resins can be used alone or in combination of two or more types.

As long as the content of the binder resin is within a range that does not impair the effects of the present invention, a film can be easily formed and good color characteristics can be easily obtained.

<Thermoplastic resin>
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of thermoplastic resins having alkali solubility include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of thermoplastic resins having alkali solubility include acrylic resins having acidic groups, α-olefin/(anhydrous) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydrous) maleic acid copolymer. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred from the viewpoint of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin is preferably a resin synthesized by the method (i) or (ii) below, for example. This further improves the crosslinking density of the film formed from the photosensitive coloring composition upon irradiation with light.

[Method (i)]
In method (i), for example, first, a polymer of an epoxy group-containing monomer and other monomers is synthesized. Next, a method of adding a carboxyl group-containing monomer to the epoxy group of the polymer, and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain an alkali-soluble resin (C2) can be mentioned.

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylate is mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

Examples of monocarboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted α-positions of (meth)acrylic acid. Examples include monocarboxylic acids such as carboxylic acid and the like.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

The monomers and polybasic acid anhydrides can be used alone or in combination of two or more.

Further, as a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Next, a method of adding an epoxy group-containing monomer to some of the carboxyl groups of the polymer to obtain an alkali-soluble resin (C2) can be mentioned.

[Method (ii)]
In method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to produce a polymer. Next, a method may be mentioned in which the hydroxyl groups of the polymer are reacted with the isocyanate groups of an isocyanate group-containing monomer.

As the hydroxyl group-containing monomer, the monomers already exemplified can be used. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because they are less likely to cause foreign matter in the coating. Further, from the viewpoint of photosensitivity, glycerol mono(meth)acrylate is preferable.

Examples of the monomer having an isocyanate group include 2-(meth)acryloyl ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

<Alkali-soluble resin without ethylenically unsaturated double bonds>
The alkali-soluble resin having no ethylenically unsaturated double bond is, for example, a resin obtained by adding an acidic group to the above-mentioned thermoplastic resin.

The weight average molecular weight (Mw) of the binder resin is preferably 2,000 or more and 40,000 or less, more preferably 3,000 or more and 30,000 or less, and even more preferably 4,000 or more and 20,000 or less. Moreover, the value of Mw/Mn (number average molecular weight) is preferably 10 or less. When the weight average molecular weight (Mw) is 2,000 or more, the adhesion to the substrate is improved and a good pattern is easily obtained. When the molecular weight is 40,000 or less, the solubility in alkali development is improved and the residue is less likely to be formed. The acid value of the alkali-soluble resin is preferably 50 mgKOH/g or more and 200 mgKOH/g or less, more preferably 70 mgKOH/g or more and 180 mgKOH/g or less, and even more preferably 90 mgKOH/g or more and 170 mgKOH/g or less, in order to impart solubility in alkali development. preferable.

Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more.

<Thermosetting compound (E)>
The thermosetting compound (E) used in the second aspect of the photosensitive coloring composition of the present invention is a compound having one or more selected from epoxy groups, oxetanyl groups, blocked isocyanate groups, and tert-butyl groups ( However, the dispersion resin (B) is excluded).
When producing a color filter using the photosensitive coloring composition of the present invention, the thermosetting compound (E) reacts during post-baking to increase the crosslinking density of the coating film. Therefore, the heat resistance of the filter segment is improved, pigment aggregation during firing of the filter segment is suppressed, and the contrast ratio is improved. Moreover, the thermosetting compound (E) does not have a carboxyl group.

The thermosetting compound may be a low-molecular compound as long as it is a compound having one or more types selected from epoxy groups, oxetanyl groups, blocked isocyanate groups, and tert-butyl groups, that is, epoxy compounds and oxetane compounds. It may also be a high molecular weight compound. However, unlike a dispersion resin such as resin (B1) that is added when dispersing a pigment, it is generally added to a dispersion liquid in which a pigment is dispersed, similarly to a polymerizable compound or a photopolymerization initiator.

Compounds containing epoxy include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, Polycondensates of various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) , polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenols and Polycondensates of ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyl) Polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.) Condensates, polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins made by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl Examples include ester-based epoxy resins.

Examples of the compound having an oxetanyl group include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or more functional oxetane compounds.

Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-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.

Bifunctional oxetane compounds include, for example, 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-oxanonan, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(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 bisphenol 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 hydrogenated bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like. Note that EO is ethyleneoxy modified, and PO is propyleneoxy modified.

Trifunctional or higher functional oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (e.g. , oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462, etc.) and a polymer obtained by radical polymerization of a (meth)acrylic monomer such as the above-mentioned OXE-30.

A blocked isocyanate group is a group having a structure in which the isocyanate group is protected by a compound called a blocking agent, and does not show reactivity as an isocyanate group at room temperature (for example, 10 to 30°C), but when heated etc. This is a group with a structure in which an isocyanate group is generated by the removal of a blocking agent from a blocked isocyanate group.

The blocked isocyanate group is more preferably a group that can generate an isocyanate group by heating at 70 to 150°C. That is, the isocyanate formation temperature of the blocked isocyanate group (blocking agent desorption temperature) is preferably 70 to 150°C. The lower limit of the isocyanate generation temperature is preferably 75°C or higher, more preferably 80°C or higher, from the viewpoint of storage stability. The upper limit of the isocyanate formation temperature is preferably 130°C or lower, more preferably 120°C or lower, from the viewpoint of curability.

The blocking agent that protects the isocyanate group of the blocked isocyanate group is, for example,
Examples include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, and the like.

Commercially available ethylenically unsaturated monomers having blocked isocyanate groups include, for example, 2-[(3,5-dimethylpyrazolyl)carboxyamino]ethyl methacrylate (Karens MOI-BP, manufactured by Showa Denko); methacrylic acid 2- Examples include (0-[1'methylpropylideneamino]carboxyamino)ethyl (Karens MOI-BM, manufactured by Showa Denko).

Examples of the compound having a tert-butyl group include tert-butyl methacrylate and tert-butyl acrylate.

Other thermosetting compounds other than compounds having one or more selected from epoxy groups, oxetanyl groups, blocked isocyanate groups, and tert-butyl groups include, for example, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, Included are melamine compounds, urea compounds, and phenolic compounds.

The thermosetting compound (E) can be used alone or in combination of two or more types.

The content of the thermosetting compound (E) is preferably 0 to 15% by mass, more preferably 5 to 10% by mass, based on the nonvolatile components of the photosensitive coloring composition.

The photosensitive coloring composition of the present invention comprises a resin (B1) having one or more types of epoxy groups and oxetanyl groups, and a thermosetting resin (B1) in a total of 100% by mass of a dispersion resin (B) and a thermosetting compound (E). In terms of heat resistance, it is preferable that the total content with compound (E) is 50 to 100% by mass.

<Photopolymerization initiator (D)>
Examples of photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1 -Hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] -2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, etc. Acetophenone compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone , 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone , isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)- s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2 -piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis (Trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6- Triazine or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O- 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 diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinones such as 9,10-phenanthrenequinone, camphorquinone, and ethyl anthraquinone Examples include borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds. Among these, oxime ester compounds are preferred.

(oxime ester compound)
When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure.

Oxime ester compounds include oximes described in JP-A No. 2007-210991, JP-A 2009-179619, JP-A 2010-037223, JP-A 2010-215575, JP-A 2011-020998, etc. Examples include ester photopolymerization initiators.

The photopolymerization initiators can be used alone or in combination of two or more types.

The content of the photopolymerization initiator is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the colorant (A). When incorporated in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
The photosensitive coloring composition of the present invention can contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinones. derivatives, polymethine dyes such as xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives , azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxy Ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4' -tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred, and 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxy Thioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethyl More preferred are carbazole and 3,6-dibenzoyl-N-ethylcarbazole.

The sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator. When contained in an appropriate amount, curability and developability are further improved.

<Thiol-based chain transfer agent>
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent as a chain transfer agent. By using a thiol-based chain transfer agent together with a photopolymerization initiator, thiyl radicals that act as a chain transfer agent and are less susceptible to polymerization inhibition by oxygen are generated in the radical polymerization process after light irradiation, so the resulting colored composition is High sensitivity.

Further, polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene and ethylene groups are preferred. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface of the pattern to the vicinity of the base material.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-Hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine Preferable examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more.

The content of the thiol chain transfer agent is preferably 0.1 to 10% by weight, more preferably 0.1 to 3% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The photosensitive coloring composition can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during exposure using photolithography, making it easier to obtain a pattern with a desired shape.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl Catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert - Alkylcatechol compounds such as butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-di-tert-butylhydroquinone and other alkylhydroquinone compounds, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin.

The content of the polymerization inhibitor is preferably 0.01 to 5% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the linearity of the taper of the pattern, the wrinkles of the coating film, the pattern resolution, etc. will be improved.

<Ultraviolet absorber>
The photosensitive coloring composition of the present invention can contain an ultraviolet absorber. The ultraviolet absorber is an organic compound having an ultraviolet absorption function, and examples thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

The content of the ultraviolet absorber is preferably 0.01 to 5% by mass based on 100% by mass nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

Benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5 -bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 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, a mixture of C7-9 side chain and linear alkyl esters, 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, methyl 3-(3- (2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1, 1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3, 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert -Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro -2H-benzotriazol-2-yl)phenyl]propionate.

Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6- Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl) -2,4-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester reaction product, 2,4-bis(2-hydroxy-4-butoxy) phenyl”-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy ) Phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris( Examples include 2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, , 2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2, Examples include 2',4,4'-tetrahydroxybenzophenone and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

<Antioxidant>
The photosensitive coloring composition of the present invention can contain an antioxidant. Antioxidants reduce the transmittance of the coating film in order to prevent the photopolymerization initiators and thermosetting compounds contained in the photosensitive coloring composition from oxidizing and yellowing due to heat curing and thermal processes during ITO annealing. You can improve.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

Antioxidants can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, transmittance, spectral characteristics, and sensitivity are improved.

<Leveling agent>
The photosensitive coloring composition of the present invention can contain a leveling agent. This improves the coating properties of the composition on the transparent substrate and the drying properties of the colored film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

The amount of surfactant added is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the nonvolatile components of the photosensitive coloring composition. When contained in an appropriate amount, the coating properties, pattern adhesion, and transmittance of the photosensitive coloring composition are improved in a well-balanced manner.

Surfactants can be used alone or in combination of two or more.

<Storage stabilizer>
The photosensitive coloring composition of the present invention can contain a storage stabilizer. This can stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, and organic acids such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include phosphine and phosphites.

The content of the storage stabilizer is preferably 0.1 to 10% by weight based on 100 parts by weight of the colorant (A).

<Adhesion improver>
The photosensitive coloring composition of the present invention can contain an adhesion improver. This improves the adhesion between the pixels and the base material, making it easier to form a fine line pattern, resulting in improved resolution.

Examples of the adhesion improver include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, - (meth)acrylic silanes such as methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyl Mercaptos such as dimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, and sulfides such as bis(triethoxysilylpropyl)tetrasulfide. and 3-isocyanate propyltriethoxysilane.

The amount of the adhesion improver used is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant (A). When used in an appropriate amount, the balance between adhesion, resolution, and sensitivity will be good.

<Solvent>
The photosensitive coloring composition of the present invention can contain a solvent. This reduces the viscosity of the composition and improves its coating properties. The solvent can be selected in consideration of the solubility, safety, etc. of each component of the photosensitive coloring composition in addition to coating properties.

As the solvent, any solvent commonly used in the field can be used, and it can be used alone or as appropriate depending on the application conditions (speed, drying conditions, etc.), taking into consideration performance such as boiling point, SP value, evaporation rate, and viscosity. used in combination.

The solvents used include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- but not -COO- in the molecule), Ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule) , -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

Among the above-mentioned solvents, it is preferable to include an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2- Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Method for manufacturing photosensitive composition>
The photosensitive coloring composition is prepared by performing a dispersion treatment using, for example, a colorant (A), a dispersion resin (B), a solvent, and the like to prepare a dispersion. When using an organic pigment, the colorant (A) can be dispersed more finely by using a dispersion aid such as a pigment derivative during dispersion treatment.Also, when the colorant has high solubility in a solvent, dispersion treatment may not be necessary. When two or more types of pigments are used together, pigment dispersions can be prepared for each pigment and then mixed. Furthermore, a pigment dispersion can be produced at once using a plurality of pigments. Next, a photopolymerizable compound (C) and a photopolymerization initiator (D) are added to the colorant dispersion and mixed to obtain a photosensitive colored composition. It goes without saying that the timing of blending each material is arbitrary.

For the dispersion treatment, a dispersion device such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor can be used.

<Removal of coarse particles>
The photosensitive coloring composition of the present invention can be produced into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably coarse particles of 1 μm or more, by centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, etc. It is preferable to remove coarse particles of 0.5 μm or more and mixed dust. As described above, the colored composition preferably does not substantially contain particles of 0.5 μm or more, more preferably 0.3 μm or less.

<Moisture content in coloring composition>
In the photosensitive coloring composition of the present invention, it is preferable that the content of water contained in the photosensitive coloring composition is 2% by mass or less.

A photosensitive coloring composition with a water content within the above range has excellent dispersion stability and sensitivity even after storage over time.

The content of water contained in the photosensitive coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, and if the water content is sufficiently small within this range, the dispersion will be stable even after storage over time. Problems with sex and sensitivity are unlikely to occur.

The method for controlling the water content is not particularly limited, and any known method can be used. Examples include a method of producing a photosensitive coloring composition while blowing dry inert gas, and a method of adding molecular sieves to dehydrate the composition after production. Among these, a method of manufacturing while blowing dry inert gas is preferred.

The water content can be measured by a known method such as the Karl Fischer method.

<Amount of toluene in the coloring composition>
The photosensitive coloring composition of the present invention may contain toluene, and when it contains toluene, the content of toluene is preferably 0.1 to 10 ppm by mass. The upper limit of the content of toluene is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and even more preferably 0.4 mass ppm or more.

<Color filter>
A color filter includes a base material (also referred to as a transparent substrate) and a filter segment formed from a photosensitive coloring composition. Preferably, the color filter has a red filter segment, a green filter segment, and a blue filter segment. Moreover, instead of these filter segments, a magenta color filter segment, a cyan color filter segment, and a yellow filter segment can be provided. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

<Production method of color filter>
It is preferable to form a color filter by first forming a black matrix on a base material, and then forming filter segments. Note that the black matrix can be formed after forming a thin film transistor (TFT) on the base material in advance. Examples of the black matrix include chromium, a multilayer film of chromium/chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light shielding agent is dispersed.

The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. The most preferred photolithography method among these will be explained.

In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain color is applied onto a transparent substrate to form a film with a dry film thickness of about 0.2 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Next, development is performed by immersing in a solvent or alkaline developer or spraying a developer, and uncured portions are removed to obtain a desired pattern. By similarly performing this step using photosensitive coloring compositions having colorants of other colors, color filters having filter segments of each color can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved. Additionally, the color filter can be heated to cure uncured photopolymerizable compounds in the filter segments.

Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Further, an antifoaming agent and a surfactant can be added to the developer.

The color filter of the present invention is attached to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is attached to the substrate as necessary. A color liquid crystal display device is manufactured by pasting it on the outside. This color liquid crystal display device supports twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convensed bend (OCB). ) can be used in a liquid crystal display mode that performs colorization using color filters.

In this specification, the color filter can be used in applications other than liquid crystal display devices, such as solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays.

<Liquid crystal display device>
The liquid crystal display device of the present invention preferably includes the color filter of the present invention, and more preferably includes a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. Among these, white LEDs are preferable because they widen the reproduction range of red.
FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including a color filter of the present invention.
The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

The liquid crystal LC is TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated). The orientation is determined according to the drive mode such as oriented birefringence. A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

A transparent protective film (not shown) is formed as necessary to cover the color filter 22 , a transparent electrode layer 23 made of ITO, for example, is formed thereon, and an alignment layer 24 is formed to cover the transparent electrode layer 23 . is provided.

Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a blue LED resin package contains a phosphor. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range from 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 is ) is 0.1 or more and 1.3 or less, or a white LED light source (LED1) that has a wavelength (λ1) with maximum emission intensity in the range of 430nm to 485nm and in the range of 530nm to 580nm. spectral characteristics having a second peak wavelength of emission intensity (λ2) within the range, and a ratio (I2/I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less. It is preferable to use a white LED light source (LED2).

Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

<Solid-state image sensor>
In this specification, a color filter can be used in a solid-state image sensor. The form used for the solid-state image sensor is not particularly limited, but for example, a plurality of photodiodes forming the light receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like are placed on a substrate. A device made of silicon nitride, etc., which has a light-shielding film on the photodiode and transfer electrode with only the light-receiving part of the photodiode open, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. The device has a protective film and a filter on the device protective film. Furthermore, there may be a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film below the filter (on the side closer to the base material), or a configuration in which the condensing means is provided on the filter. It's okay. Further, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition wall preferably has a low refractive index for each colored pixel.
An imaging device equipped with the solid-state imaging device of the present invention can be used in various applications such as, for example, a digital camera, an electronic device having an imaging function (smartphone, tablet terminal, etc.), an in-vehicle camera, a surveillance camera, an optical sensor, and the like.

The present invention will be explained below with reference to Examples. However, the present invention is not limited to the examples. In addition, "part" in an Example represents "mass part", and "%" represents "mass %."

Prior to Examples, a calculation method for measuring the average molecular weight of the resin and the acid value of the resin will be explained.

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured by a general method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle diameter of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was determined by approximating a rectangular parallelepiped of the determined particle size, and the volume average particle size was determined as the average primary particle size.

(Dispersed particle size measurement)
Using Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs dynamic light scattering method (FFT power spectrum method), the particle permeability is set to absorption mode, the particle shape is non-spherical, and the average diameter is calculated by rounding D50 to the nearest 5 nm. And so. The dilution solvent used for the measurement was the same as that used for the dispersion, and the measurement was performed on the sample treated with ultrasonic waves immediately after sample preparation.

(Average molecular weight of resin)
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use an automatic titration device ("COM-555" manufactured by Hiranuma Sangyo) using 0.1 mol/L KOH aqueous solution as the titrant. ) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

<Method for producing colorant>
(Coloring agent (A-1))
Diketopyrrolopyrrole red pigment C. I. 200 parts of Pigment Red 254 ("B-CF" manufactured by BASF Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. Next, this kneaded material was poured into 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 85°C overnight. , 190 parts of colorant (A-1) were obtained.

(Colorant (A-2))
Anthraquinone red pigment C. I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Shinic Co., Ltd.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. did. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. Colorant (A-2) was obtained.

(Colorant (A-3))
C. 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 placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 5 hours. . This mixture was poured into 4000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove the salt and solvent, the mixture was heated to about 80°C for 24 hours. It was dried to obtain a colorant (A-3).

(Colorant (A-4))
Phthalocyanine green pigment C. I. 100 parts of Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70° C. for 6 hours. This kneaded material was poured into 3000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and colored. 97 parts of agent (A-4) were obtained.

(Colorant (A-5))
Phthalocyanine green pigment C. I. 500 parts of Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120° C. for 4 hours. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. 490 parts of colorant (A-5) were obtained.

(Colorant (A-6))
C. I. Pigment Yellow 139 (“Irgafore Yellow” manufactured by BASF Japan)
2R-CF''), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded material was poured into 3,000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and colored. Agent (A-6) was obtained.

(Colorant (A-7))
100 parts of a metal complex yellow pigment (C.I. Pigment Yellow 150, "Yellow Pigment E4GN" manufactured by LANXESS), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho). The mixture was kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a colorant (A-7).

(Colorant (A-8))
An azobarbituric acid precursor was prepared according to the synthesis method described in JP-A-2017-171915. (Instruction 1) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were introduced into 1100 parts of distilled water at 85°C. The pH was then adjusted to approximately pH 5 using an aqueous potassium hydroxide solution and stirring continued for 90 minutes.
Azobarbituric acid (0.3 mol) prepared in Instruction 1 was then mixed with 1500 parts of distilled water at 82°C. Then 10 parts of 30% hydrochloric acid were added dropwise to adjust the pH to 2-2.5. Thereafter, 79.4 parts of melamine (0.63 mol) were added. A mixed solution of 0.225 mol of 25% nickel chloride + 0.075 mol of 25% zinc chloride was then added dropwise. After 3 hours at 82°C, the pH was adjusted to about 5.5 using aqueous potassium hydroxide. This was followed by dilution with approximately 100 parts of distilled water at 90°C. Then, 21 parts of 30% hydrochloric acid were added dropwise and the temperature was maintained at 90° C. for 12 hours. The pH was then adjusted to about 5 using an aqueous potassium hydroxide solution. The pigment was then isolated on a suction filter, washed, dried in a vacuum drying cabinet at 80°C, and ground for 2 minutes in a standard laboratory mill to give the zinc/nickel azobarbiturate. A hybrid compound was obtained having the following components: melamine adduct of acid, 25 mol% Zn and 75 mol% nickel.
100 parts of the above hybrid compound, 10 parts of the dye derivative (d-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70° C. for 8 hours. This mixture was poured into 2000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove the salt and solvent, and then heated at 80°C for 24 hours. It was dried to obtain a colorant (A-8).

(Colorant (A-9))
C. I. 50 parts of Pigment Yellow 185 ("Paliotol Yellow L 1155" manufactured by BASF Japan), 250 parts of sodium chloride, and 25 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 100° C. for 6 hours. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. , a colorant (A-9) was obtained.

(Colorant (A-10))
Blue pigment C. I. 100 parts of Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and heated at 70°C for 12 hours. Kneaded. This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then heated to 80°C for 24 hours. It was dried to obtain 98 parts of colorant (A-10).

(Coloring agent (A-11))
Phthalocyanine blue pigment C. I. Pigment Blue 15:3 (PB15:3, 200 parts of "LIONOL BLUE FG-7351" manufactured by Toyo Color Co., Ltd., 600 parts of sodium chloride, and 600 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and heated at 80°C. Next, this kneaded product was poured into 8,000 parts of warm water and stirred for 8 hours while heating to 120°C to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, It was dried at 85°C for a day and night to obtain a colorant (A-11).

(Colorant (A-12))
Purple pigment C. I. 100 parts of Pigment Violet 23 (“LIONOGENVIOLET FG-6140” manufactured by Toyo Color Co., Ltd.), 800 parts of crushed common salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. . This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then heated to 80°C for 24 hours. It was dried to obtain 95 parts of colorant (A-12).

Table 1 shows the average primary particle diameter (nm) of each finely divided colorant.

<Production method of colorant (dye)>
(Resin 1 having a cationic group in the side chain)
67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile) ) and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-neck separable flask, and added dropwise over 2 hours. Two hours after completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more based on nonvolatile components and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added and reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, a resin 1 was obtained in which the resin component had 47% by mass of ammonium groups and a cationic group in the side chain. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 01 (AR52-JK))
C. by following the steps below. I. Dye 01 (AR52-JK), which is a salt-forming compound consisting of Acid Red 52 and Resin 1 having a cationic group in its side chain, was produced.
30 parts (calculated as non-volatile content) of Resin 1 having a cationic group in the side chain were added to 2000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the resin solution. After the dropwise addition, the mixture was stirred at 60° C. for 120 minutes to fully react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be the end point when there was no bleeding, and it was determined that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing water in a drier, and 32 parts of C.I. I. Dye 01 (AR52-JK), which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain, was obtained. At this time, C.I. in Dye 01 (AR52-JK) I. The content of the effective pigment component derived from Acid Red 52 was 25% by mass.

<Method for producing colorant (dye) solution>
(Dye solution (DS-01))
The following mixture was stirred and mixed to be uniform, and then filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (DS-01).
Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

<Basic dye derivative>
Basic dye derivatives were used as described below.

Basic dye derivative (1)

Basic dye derivative (2)


Basic dye derivative (3)

Basic dye derivative (4)



However, Me represents a methyl group.

Basic dye derivative (5)


However, Et represents an ethyl group.

<Manufacture of dispersed resin (B)>
(Production of dispersion resin (B1-1) liquid)
In a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 80 parts of t-butyl acrylate, 15 parts of acrylic acid, 35 parts of methoxyethyl acrylate, 70 parts of ETERNACOLLOXMA (manufactured by Ube Industries, Ltd.), and propylene glycol monomethyl ether acetate. 100 parts were charged and the atmosphere was replaced with nitrogen gas. Heat the inside of the reaction vessel to 80°C and add a solution of 0.1 part of 2,2'-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol. The mixture was reacted for 10 hours. It was confirmed by non-volatile content measurement that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene dioic anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N) Hydroxyl value: 112 mgKOH/g, manufactured by Kuraray Co., Ltd.) 106 parts, 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst. The mixture was added and reacted at 100°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The non-volatile content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-1) liquid having an acid value of 90 mgKOH/g and a weight average molecular weight of 14,000.

(Production of dispersion resin (B1-2) liquid)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 40 parts of n-butyl acrylate, 40 parts of 2-methoxyethyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, Karenz MOI-BM (Showa Denko) (manufactured by Ube Industries, Ltd.), 20 parts of ETERNA COLLOXMA (manufactured by Ube Industries, Ltd.), and 100 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was replaced with nitrogen gas. Heat the inside of the reaction vessel to 80°C and add a solution of 0.1 part of 2,2'-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol. The mixture was reacted for 10 hours. It was confirmed by non-volatile content measurement that 95% had reacted. Next, BPAF: 39 parts of 9,9-bis(3,4-dicarboxyphenyl)fluorene dioic anhydride (manufactured by JFE Chemical Co., Ltd.), C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N) Hydroxyl value: 112 mgKOH/g, manufactured by Kuraray Co., Ltd.) 106 parts, 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst. The mixture was added and reacted at 100°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The nonvolatile content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-2) liquid having an acid value of 94 mgKOH/g and a weight average molecular weight of 22,000.

(Production of dispersion resin (B1-3) liquid)
3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of propylene glycol monomethyl ether acetate, and dimethylbenzylamine were placed in a reaction tank equipped with a gas introduction tube, condenser, stirring blade, and thermometer. 0.1 part was charged. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Additionally, 30 parts of t-butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl) methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of propylene glycol monomethyl ether acetate. was charged, and 0.2 part of 2,2'-azobisisobutyronitrile was added every 30 minutes in 15 portions while maintaining the inside of the reaction vessel at 80°C. One hour after the final addition, non-volatile content was measured and it was confirmed that 95% of the monomers had reacted. It was diluted by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 40% by nonvolatile fractionation, and a dispersion resin (B1) having a carboxyl group with an acid value per nonvolatile content of 51 mgKOH/g and a weight average molecular weight (Mn) of 24,000 was prepared. -3) A liquid was obtained.

(Production of dispersion resin (B1-4 to 8) liquid)
Dispersed resin (B1-4 to B1-8) solutions were obtained by synthesizing and adjusting in the same manner as the dispersion resin (B1-3) solution, except that the blending amounts were changed as shown in Table 2-1.

<Abbreviations in the table>
PGMAc: Propylene glycol monomethyl ether acetate tBA: tert-butyl acrylate OXMA: ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, manufactured by Ube Industries, Ltd.)
MAA: Methacrylic acid EA: Ethyl acrylate MMA: Methyl methacrylate AIBN: 2,2'-azobisisobutyronitrile

(Production of dispersion resin (B1-9) liquid)
6 parts of trimellitic anhydride, 2 parts of 3-mercapto-1,2-propanediol, 50 parts of methoxypropyl acetate, and 0.0 parts of dimethylbenzylamine were placed in a reaction tank equipped with a gas inlet tube, condenser, stirring blade, and thermometer. I prepared one part. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Furthermore, 20 parts of 2-hydroxyethyl methacrylate, 30 parts of t-butyl acrylate, 20 parts of ETERNACOLL OXMA (3-ethyl-3-oxetanyl) methyl methacrylate (manufactured by Ube Industries), 5 parts of methacrylic acid, and 25 parts of ethyl acrylate were added. While maintaining the inside of the reaction vessel at 80°C, 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes. One hour after the final addition, non-volatile content was measured and it was confirmed that 95% of the monomers had reacted. Next, it was diluted with 60 parts of methoxypropyl acetate. Thereafter, 2-methacryloyloxyethyl isocyanate, 24 parts of Showa Denko, 0.1 part of hydroquinone, and 29 parts of methoxypropyl acetate were charged, and the inside of the reactor was heated to 70°C and reacted for 4 hours. After confirming the disappearance of the peak at 2270 cm-1 based on isocyanate groups by IR, the reaction was completed by diluting with 37 parts of methoxypropyl acetate. A dispersion resin (B1-9) liquid was obtained with a nonvolatile content of 40%, an acid value per nonvolatile content of 51 mgKOH/g, and a weight average molecular weight (Mw) of 15,000.

(Production of dispersion resin (B1-10 to 12) liquid)
Dispersed resin (B1-10 to B1-12) solutions were obtained by synthesizing and adjusting the non-volatile content in the same manner as the dispersion resin (B1-9) solution, except that the blending amounts were changed as shown in Table 2-2.

<Abbreviations in the table>
HEMA: 2-hydroxyethyl methacrylate GLM: 2,3-dihydroxypropyl 2-methylpropenoate (manufactured by NOF Corporation: Bremmer GLM)
MOI: 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz MOI)
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko: Karenz AOI)
BEI: 1,1-bis(acryloyloxymethyl)ethyl isocyanate (manufactured by Showa Denko: Karenz BEI)

(Production of dispersion resin (B1-13) liquid)
In a reaction vessel equipped with a gas introduction pipe, thermometer, condenser, and stirrer, 70 parts of ETERNACOLL OXMA (manufactured by Ube Industries), 90 parts of t-butyl acrylate, 30 parts of methoxyethyl acrylate, 10 parts of acrylic acid, and propylene glycol monomethyl ether acetate were added. 50 parts and 50 parts of cyclohexanone were charged, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution of 0.1 part of 2,2'-azobisisobutyronitrile dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Time reacted. It was confirmed by solid content measurement that 95% had reacted. Next, 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 were added as a catalyst. The reaction was carried out at 100°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-13) liquid having an acid value of 76 mgKOH/g and a weight average molecular weight of 8,000.

(Production of dispersion resin (B1-14) liquid)
In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 60 parts of ETERNACOLL OXMA (manufactured by Ube Industries), 50 parts of t-butyl acrylate, 60 parts of t-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 10 parts of methacrylic acid were added. 1 part, 50 parts of propylene glycol monomethyl ether acetate, and 50 parts of cyclohexanone were charged, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution of 0.1 part of 2,2'-azobisisobutyronitrile dissolved in 12 parts of 3-mercapto-1,2-propanediol was added. Time reacted. It was confirmed by solid content measurement that 95% had reacted. Next, 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 were added as a catalyst. The reaction was carried out at 100°C for 7 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-14) liquid having an acid value of 70 mgKOH/g and a weight average molecular weight of 14,000.

(Production of dispersion resin (B2-1) liquid): In a reaction vessel equipped with a gas inlet pipe having no thermally crosslinkable group, a temperature control, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, and isobornyl methacrylate 20 parts of n-butyl methacrylate, 30 parts of methyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was replaced with nitrogen gas. The inside of 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 a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate. It was confirmed by solid content measurement that 95% had reacted. Added 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, and heated at 100°C. The reaction was allowed to proceed for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was completed, and the solid content was diluted by adding propylene glycol monomethyl ether acetate so that the solid content was 40%. A dispersion resin (B2-1) liquid having a value of 70 mgKOH/g and a weight average molecular weight of 8,400 was obtained.

<Example of manufacturing binder resin>
(Preparation of binder resin (bi) liquid)
196 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. 196 parts of cyclohexanone was then heated to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (bi) liquid was prepared. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (BP) liquid)
370 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80°C, and the inside of the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (equivalent to 100 mol% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 part of hydroquinone were added to the container, and 120 The reaction was continued at ℃ for 6 hours, and the reaction was terminated when the non-volatile acid value reached 0.5 to obtain a solution of acrylic resin. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (equivalent to 100 mol % of the generated hydroxyl groups) and 0.5 part of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (bf) liquid was prepared. The weight average molecular weight (Mw) was 19,000.

<Method for producing colored composition>
[Manufacture example 1]
(Manufacture of colored composition (single color: R-1))
The following mixture was stirred and mixed until it was homogeneous, and then dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was filtered through a 0 μm filter to produce a colored composition (R-1) containing 26% by mass of non-volatile components.
Colorant (finely divided pigment: A-1): 20.0 parts Dispersed resin (B1-1: non-volatile content 40.0% liquid): 15.0 parts Solvent (N): 65.0 parts

[Production Examples 2 to 36]
(Manufacture of colored compositions (R-2 to R-36))
Colored compositions (R-2 to R-36) were prepared in the same manner as colored composition (R-1) except that the compositions were changed to those shown in Table 3-1 and Table 3-2.

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (X-1).
Coloring composition (R-1: nonvolatile content 26.0%): 70.0 parts Photopolymerizable monomer (C-1) Ring structure-containing polyfunctional acrylate: 3.0 parts Photopolymerization initiator (D): 1.8 parts Sensitizer (F): 0.2 parts Thiol chain transfer agent (G): 0.4 parts Polymerization inhibitor (H): 0.1 part Ultraviolet absorber (I): 0.1 part Antioxidant (J): 0.1 part Leveling agent (K: 3% non-volatile content): 1.0 part Storage stabilizer (L): 0.1 part Silane coupling agent (M): 0.2 part Solvent (N): 23.0 copies

[Examples 2 to 50, Comparative Examples 1 to 3]
(Preparation of photosensitive coloring compositions (X-2 to 53))
The same procedure as in Example 1 was carried out except that the types of the coloring composition and binder resin solution in Example 1 were changed as described in Tables 4-1 and 4-2, and photosensitive coloring compositions (X-2 to 53 ) were prepared respectively. In this specification, Example 6 is a reference example. Further, the details of each raw material are as follows.

<Polymerizable compound (C)>
(C-1) Hydrocarbon ring-containing polyfunctional polyester acrylate



Ac: acryloyl group

(C-2) Hydrocarbon ring-containing polyfunctional polyester acrylate


Ac: acryloyl group

(C-3) Hydrocarbon ring-containing polyfunctional polyester acrylate


Ac: acryloyl group

(Polymerizable compound (CM))
Hereinafter, (C-4) to (C-10) were mixed in the same amount to form a polymerizable compound (CM).
(C-4) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]
(C-5) Dipentaerythritol penta and hexaacrylate [Aronix M402 (manufactured by Toagosei Co., Ltd.)]
(C-6) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)]
(C-7) Caprolactone modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

(C-8) Polyfunctional urethane acrylate synthesized by the method below. Pentaerythritol triacrylate (432 g and hexamethylene diisocyanate 84 g) were charged into a 5-necked reaction vessel with a content of 1 liter, and reacted at 60°C for 8 hours. ) A product containing a polyfunctional urethane acrylate (C-8) having an acryloyl group was obtained.The proportion of the polyfunctional urethane acrylate (C-8) in the product was 70% by mass, and the remainder was It was confirmed by IR analysis that no isocyanate group was present in the reaction product.

(C-9) Bifunctional bisphenol A type (meth)acrylate [ABE-300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
(C-10) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]

<Photopolymerization initiator (D)>
(D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan)]
(D-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan)]
(D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by Ciba Japan)]
(D-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(D-5) p-dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)]
(D-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(D-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (manufactured by BASF Japan)]
(D-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan)]
The above (D-1) to (D-8) were mixed in the same amount to prepare a photopolymerization initiator (D).

<Thermosetting compound (E)>
(Epoxy compound (E-1))
(E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)],
(E-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX)],
(E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were mixed in equal amounts to prepare an epoxy compound (E-1).
(Oxetane compound (E-2))
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aronoxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Sensitizer (F)>
(F-1) 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(F-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (F-1) and (F-2) were mixed in the same amount to prepare a sensitizer (F).

<Thiol chain transfer agent (G)>
(G-1) Trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(G-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
Above, (G-1) to (G-5) were mixed in the same amount, and the thiol-based chain transfer agent (G) was prepared.
And so.

<Polymerization inhibitor (H)>
(H-1) 3-methylcatechol (H-2) Methylhydroquinone (H-3) tert-butylhydroquinone Above, (H-1) to (H-3) are mixed in equal amounts, and a polymerization inhibitor is added. (H).

<Ultraviolet absorber (I)>
(I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine [TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)]
The above (I-1) and (I-2) were mixed in the same amount to prepare an ultraviolet absorbent (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (J-2) Dioctadecyl 3,3'-thiodipropanoate (J-3) Tris[2 , 4-di-(tert)-butylphenyl]phosphine (J-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate, (J -1) to (J-5) were mixed in the same amount to prepare an antioxidant (J).

<Leveling agent (K)>
BYK-330 manufactured by BYK Chemie Co., Ltd. 1 copy,
1 copy of "Megafac F-551" manufactured by DIC,
A mixed solution in which 1 part of "Emulgen 103" manufactured by Kao Corporation was dissolved in 97 parts of propylene glycol monomethyl ether acetate.

<Storage stabilizer (L)>
(L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
As described above, (L-1) and (L-2) were mixed in the same amount to prepare a storage stabilizer (L).

<Adhesion improver (M)>
(M-1) 3-glycidoxypropyltriethoxysilane [Shin-Etsu silicone silane coupling agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane [Shin-Etsu silicone silane coupling agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu silicone silane coupling agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-mercaptopropyltrimethoxysilane [Shin-Etsu silicone silane coupling agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (M-1) to (M-4) were mixed in the same amount to prepare an adhesion improver (M).

<Solvent (N)>
(N-1) Cyclohexanone 20 parts (N-2) Ethyl 3-ethoxypropionate 20 parts (N-3) Propylene glycol monomethyl ether 20 parts (N-4) Cyclohexanol acetate 20 parts (N-5) Dipropylene glycol 20 parts (N-1) to (N-5) of methyl ether acetate were mixed in the above mass parts to prepare a solvent (N).

<Evaluation of photosensitive coloring composition>
Each test was conducted in the following manner. The results of the test are shown in Table 5.
The evaluation criteria are as follows.
5: Very good.
4: Excellent.
3: Slightly excellent.
2: Practical 1: Not practical

<Measurement of viscosity characteristics>
The viscosity of the photosensitive coloring compositions obtained in Examples and Comparative Examples was measured at a rotation speed of 20 rpm using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.).
The evaluation ranks are as follows.
5: Viscosity 2.0 or more and less than 10.0
1: Viscosity 10.0 or more

(Storage stability)
The storage stability of the photosensitive coloring compositions obtained in Examples and Comparative Examples was evaluated by the following method. The initial viscosity on the next day after preparing the photosensitive coloring composition and the aging viscosity after aging at 40°C for one week were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The measurement was carried out at a temperature of 50 rpm. From the values of the initial viscosity and the viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
5: Change rate less than 50%
1: Change rate of 50% or more

(Heat-resistant)
Heat resistance was evaluated by spectral change, film shrinkage rate, and cracks as shown below.
[Evaluation of spectral changes]
The photosensitive coloring compositions obtained in Examples and Comparative Examples were applied by spin coating onto a glass substrate, dried (prebaked) at 100°C for 120 seconds using a hot plate, and then dried at 200°C for 30 seconds using an oven. A film having a thickness of 0.60 μm was produced by heating for 30 minutes (post-baking). The transmittance Tr1 of the obtained film at a wavelength of 450 nm was measured using a Cary 5000 UV-Vis-NIR spectrophotometer (manufactured by Agilent Technologies). Next, the obtained film was heat-treated at 300° C. for 5 hours in a nitrogen atmosphere. The transmittance Tr2 of the film after the heat treatment at a wavelength of 450 nm was measured.
The absolute value ΔT of the difference between Tr1 and Tr2 was calculated, and the spectral change was evaluated according to the following evaluation criteria. The evaluation results are listed in the "Spectral Change" column of Table 14. It can be said that the smaller ΔT is, the less likely a spectral change will occur, which is preferable. Both Tr1 and Tr2 were measured in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, with the substrate temperature adjusted to 25°C.

-Evaluation criteria-
5: ΔT was 0.1% or less.
4: ΔT exceeded 0.1% and was 0.5% or less.
3: ΔT exceeded 0.5% and was 1% or less.
2: ΔT was more than 1% and less than 5%.
1: ΔT exceeded 5%.

[Evaluation of membrane shrinkage rate]
The photosensitive coloring compositions obtained in Examples and Comparative Examples were applied by spin coating onto a glass substrate, dried (prebaked) at 100°C for 120 seconds using a hot plate, and then dried at 200°C for 30 seconds using an oven. A film having a thickness of 0.60 μm was produced by heating for 30 minutes (post-baking). The film thickness is measured by scraping a part of the film to expose the glass substrate surface, and measuring the level difference between the glass substrate surface and the coated film (film thickness of the coated film) using a stylus-type level difference meter (DektakXT, manufactured by BRUKER). did. Next, the obtained film was heat-treated at 300° C. for 5 hours in a nitrogen atmosphere. The film thickness of the film after the heat treatment was measured in the same manner, the film shrinkage rate was determined from the following formula, and the film shrinkage rate was evaluated according to the following evaluation criteria. The evaluation results are listed in the column of "Membrane shrinkage rate" in Table 14. Both T0 and T1 below were measured in a laboratory where the temperature and humidity were controlled at 22±5°C and 60±20%, with the substrate temperature adjusted to 25°C. The smaller the membrane contraction rate, the more suppressed the membrane contraction is, which is a preferable result.
Membrane shrinkage rate (%) = (1-(T1/T0)) x 100
T0: Thickness of the film immediately after production (=0.60 μm)
T1: Film thickness after heat treatment at 300°C for 5 hours in a nitrogen atmosphere - Evaluation criteria -
5: Membrane shrinkage rate was 1% or less.
4: The membrane shrinkage rate was more than 1% and less than 5%.
3: The membrane shrinkage rate was more than 5% and less than 10%.
2: The membrane shrinkage rate was more than 10% and less than 30%.
1: Membrane shrinkage rate exceeded 30%.

[Crack evaluation]
The photosensitive coloring compositions obtained in Examples and Comparative Examples were applied by spin coating onto a glass substrate, dried (prebaked) at 100°C for 120 seconds using a hot plate, and then dried at 200°C for 30 seconds using an oven. A film having a thickness of 0.60 μm was produced by heating for 30 minutes (post-baking).
Next, 200 nm of SiO2 was deposited on the surface of the obtained film by sputtering to form an inorganic film. The film on which the inorganic film was formed was heat-treated at 300° C. for 5 hours in a nitrogen atmosphere. The surface of the inorganic film after the heat treatment was observed with an optical microscope, the number of cracks per 1 cm 2 was counted, and the presence or absence of cracks was evaluated according to the following evaluation criteria. The evaluation results are listed in the "Crack" column of Table 14.
-Evaluation criteria-
5: The number of cracks per 1 cm ² was 0.
4: The number of cracks per 1 cm ² was 1 to 10.
3: The number of cracks per 1 cm ² was 11 to 50.
2: The number of cracks per 1 cm ² was 51 to 100.
1: The number of cracks per 1 cm ² was 101 or more.

(Developability: Residue)
The photosensitive coloring compositions obtained in Examples and Comparative Examples were spin-coated onto a glass substrate using a spin coater so that the dry film thickness was 1.0 μm, and dried at 70° C. for 20 minutes. Next, the dried coating film was exposed to light at 200 mJ/cm 2 using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW/cm 2 through a photomask having a 6 μm square mask pattern arranged thereon.

The unexposed areas of the pattern-exposed coating film were developed using a 2% by weight aqueous potassium hydroxide solution, and then washed with pure water. Thereafter, the water droplets were blown off with high-pressure air, the substrate was naturally dried, and a post-baking process was performed on a hot plate at 230° C. for 30 minutes to form a pattern on the glass substrate.

The colored composition pattern for color filters prepared in the above pattern peelability evaluation was cut out using a glass cutter, and was examined using a scanning electron microscope (S-4800, manufactured by Hitachi) at a magnification of 15,000.
It was observed at 0x magnification and evaluated according to the following evaluation criteria.
5: There is no residue on the pattern with a line width of 6 μm. 3: There is a small amount of residue on the pattern with a line width of 6 μm. 1: There is a lot of residue on the pattern with a line width of 6 μm.

10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (7)

A photosensitive coloring composition comprising a colorant (A), a dispersion resin (B), a photopolymerizable compound (C), and a photoinitiator (D),
The dispersion resin (B) contains a resin (B1) having one or more thermosetting groups selected from an oxetanyl group and a blocked isocyanate group,
The photopolymerizable compound (C) is an ester bond-containing hydrocarbon ring-containing polyfunctional acrylate of the compound represented by the following general formula (1) (however, an ester bond-containing hydrocarbon ring-containing polyfunctional acrylate having a weight average molecular weight of 2000 or more ) (excluding acrylates).
General formula (1)

The symbols in general formula (1) are as follows.
The photosensitive coloring according to claim 1, wherein the ester bond-containing hydrocarbon ring-containing polyfunctional acrylate is a compound having an ester bond between a polyhydric alcohol (X) and a polybasic acid (Y) having a cyclic structure. Composition. The photosensitive coloring composition according to claim 1, wherein the content of the ester bond-containing hydrocarbon ring-containing polyfunctional acrylate is 25 to 75% by mass based on 100% by mass of the photopolymerizable compound (C). The photosensitive coloring composition according to claim 1, wherein the ester bond-containing hydrocarbon ring-containing polyfunctional acrylate contains a compound containing a structural unit derived from an isocyanurate ring. A color filter comprising a base material and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 4. A liquid crystal display device comprising the color filter according to claim 5. A solid-state imaging device comprising the color filter according to claim 5.