Photosensitive coloring composition, color filter, liquid crystal display device, and solid-state imaging element

Abstract

To achieve high printing density and excellent durability without an ink-receiving layer, while enabling high-speed printing without causing inkjet ejection defects.SOLUTION: A photosensitive coloring composition comprises a colorant, a resin-type dispersant, a binder resin, a polymerizable compound, and a photopolymerization initiator, where the colorant contains a pigment represented by the general formula in the figure.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive coloring composition that uses pulsed exposure to ultraviolet light with a wavelength of 250 nm or less. [Background technology]

[0002] Solid-state imaging devices such as CCD (charge-coupled device) and CMOS (complementary metal-oxide semiconductor) are used in smartphones, tablet terminals, and various sensors. Color filters having pixels formed using photosensitive coloring compositions are used in solid-state imaging devices. It is necessary to reduce the pixel size of color filters in order to increase the pixel count of solid-state imaging devices and improve image quality.

[0003] Therefore, Patent Document 1 discloses a photosensitive coloring composition containing CI Pigment Red 254, which uses light with a wavelength of 300 nm or less for photocuring. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2012-532334 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in conventional photosensitive coloring compositions, the color density decreases as the pixel thickness is reduced, while the method of increasing the concentration of the colorant results in a relatively small amount of photosensitive material and binder resin, which causes problems such as reduced developability, rectangularity of the pixel side surface, and adhesion to the base material (substrate).

[0006] An object of the present invention is to provide a photosensitive coloring composition which has high developability, excellent rectangular shape and adhesion, and is capable of forming pixels with good color density. [Means for solving the problem]

[0007] <1> The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for a color filter that forms a pattern by pulse exposure to ultraviolet light having a wavelength of 250 nm or less, The composition includes a colorant (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), The colorant (A) is characterized by containing a pigment (A1) represented by the following general formula (1) and a yellow colorant (A3). General formula (1) [ka]

[0008] (In general formula (1), R 1 each independently represents any one of a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an alkylamino group, and an amino group. <2> The resin-type dispersant (B) includes a resin-type dispersant (B1-R) having an aromatic carboxylate moiety and a vinyl polymer moiety, and the aromatic carboxylate moiety has a terminal-capping moiety derived from an end-capping material. <1> The photosensitive coloring composition according to claim 1. <3> The photopolymerization initiator (E) contains one or more oxime ester compounds selected from the group consisting of the following (E1), (E2), and (E3): <1> ,or <2> The photosensitive coloring composition according to claim 1. (E1) Compound having two oxime ester groups and a carbazole skeleton (E2) Compounds having two oxime ester groups and a phenothiazine skeleton (E3) A compound represented by the following general formula (2): General formula (2) [ka] (In general formula (2), R 2 R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.3 R represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 4 R represents a branched alkyl group or a cyclic organic group having 6 or more carbon atoms. 5 represents a monovalent substituent (excluding an oxime ester group); and n represents an integer of 0 to 3. <4> The polymerizable compound (D) includes a compound (D1) represented by the following general formula (3): <1> ~ <3> The photosensitive coloring composition according to any one of the above. General formula (3) [ka] (In the general formula (3), X is a partial structure represented by the following general formula (4), general formula (5), or general formula (6). R 1 , R 2 represents a hydrogen atom or a methyl group. [ka] In the general formula (4), n represents an integer of 1 to 4, and R 3 represents a hydrogen atom or a methyl group. In general formula (5), n represents an integer of 1 to 4. In general formula (6), n represents an integer of 1 to 4. <5> <1> ~ <4> A color filter having filter segments formed from the photosensitive coloring composition according to any one of the preceding claims. <6> <5> A solid-state imaging device comprising the color filter according to claim 1. <7> <5> A liquid crystal display device comprising the color filter according to claim 1. Effect of the Invention

[0009] According to the present invention, it is possible to provide a photosensitive coloring composition that has high developability, excellent rectangular shape and adhesion, and can form pixels with good color density. The present invention also provides a color filter, a solid-state imaging device, a liquid crystal display device, etc. [Brief description of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this specification means Color Index (CI). Colorants include pigments and dyes. EO is an abbreviation for ethyleneoxy, and PO is an abbreviation for propyleneoxy. A monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is in a state in which a monomer forms a resin after polymerization.

[0012] The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for a color filter that forms a pattern by pulse exposure to ultraviolet light having a wavelength of 250 nm or less, The composition includes a colorant (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), The colorant (A) is characterized by containing a pigment (A1) represented by the following general formula (1) and a yellow colorant (A3).

[0013] The pigment (A1) represented by the general formula (1) used in the photosensitive coloring composition of the present invention has a higher coloring power than other diketopyrrolopyrrole pigments, so that good color density can be obtained without significantly increasing the concentration in the thin film pixel. In addition, since the colorant in the pixel is not significantly increased in concentration, it is not necessary to suppress the content of the binder resin and the polymerizable compound. As a result, even when forming fine pixels, it is possible to form pixels that have high developability, rectangularity, and excellent adhesion.

[0014] <Pulse exposure to ultraviolet light> Examples of ultraviolet light pulse exposure include excimer lasers that generate laser light using a mixture of rare gases such as argon, krypton, and xenon and halogen gases such as fluorine and chlorine. The oscillation wavelength varies depending on the combination of the types of the mixed gas, and includes 193 nm (ArF), 248 nm (KrF), 308 nm (XeCl), and 351 nm (XeF). Among these, the present invention prefers pulse exposure with an excimer laser with a wavelength of 248 nm (KrF). The excimer laser has a pulse width of several tens of ns, and the cross section of the beam reflects the shape of the discharge area, oscillating a rectangular beam with high output. There are also devices that can output pulse energy of up to several thousand mJ. Excimer lasers are more suitable for fields where a relatively large area is processed at once with high irradiation intensity than processing where the beam is concentrated at one point, and are used in the field of laser processing.

[0015] In general, an excimer laser is a laser that utilizes the radiation from excimer molecules that exist for a very short time when the mixed gas is excited, and the ground level of the excimer is in a dissociated state. Therefore, the ground molecular density is always zero, making it a very good laser medium, and it is possible to form pixels with excellent surface morphology.

[0016] As described above, the excimer laser is an excellent laser medium capable of forming filter segments with excellent surface morphology in a short time of a few tens of nanoseconds. However, matching with the composition to be cured is necessary. Depending on the combination of pigments, monomers having ethylenically unsaturated double bonds, and photopolymerization initiators that make up the composition, the polymerizable compound on the surface of the colored coating film on the side irradiated with the excimer laser cures instantaneously, while the curing of the inside of the coating film is somewhat delayed, and therefore the difference in curing speed can cause issues with the rectangularity of the pixels and adhesion to the substrate.

[0017] <Colorant (A)> The colorant (A) contains a pigment (A1) represented by the following general formula (1) and a yellow colorant (A3). General formula (1) [ka]

[0018] In general formula (1), R 1 each independently represents any one of a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an alkylamino group, and an amino group. Examples of the pigment (A1) represented by general formula (1) include the following (a1-1) to (a1-9). Among these, the compound represented by (a1-1) (CI Pigment Red 272) is preferred in terms of further improving coloring strength.

[0019] [ka] [ka] [ka]

[0020] The content of the pigment (A1) is preferably 20% by mass or more, more preferably 30% by mass or more, based on the nonvolatile content of the photosensitive coloring composition. The upper limit of the content is preferably 70% by mass or less.

[0021] The content of the pigment (A1) is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on 100% by mass of the colorant (A). The content is preferably 95% by mass or less, and more preferably 85% by mass or less. The content of the colorant (A) is preferably from 30 to 80 mass %, more preferably from 40 to 70 mass %, of the non-volatile content of the photosensitive color composition.

[0022] <Yellow color material (A3)> The photosensitive coloring composition of the present invention contains a yellow coloring material (A3) in addition to the pigment (A1) from the viewpoint of adjusting the hue. The yellow coloring material may be a yellow pigment or a yellow dye.

[0023] (Yellow pigment) Yellow pigments include, for example, CI 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, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 1,152, 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, JP2012-226110A, JP2017-171912A, JP2017-171913A, JP2017-171914A, JP2017-171915A, and the like. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110 are preferred.

[0024] (yellow dye) Examples of yellow dyes include quinoline dyes, azo dyes, disazo dyes, methine dyes, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, and quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228.

[0025] Among these, the yellow colorant (A3) is preferably CI Pigment Yellow 139 from the viewpoints of heat resistance, light fastness, and transmittance.

[0026] The content of the yellow coloring material (A3) is preferably 5% by mass or more, more preferably 10% by mass or more, based on the non-volatile content of the photosensitive coloring composition, and the upper limit of the content is preferably 30% by mass or less.

[0027] The mass ratio of the pigment (A1) represented by the general formula (1) to the yellow colorant (A3) is preferably from 9 / 1 to 3 / 7, and more preferably from 9 / 1 to 5 / 5.

[0028] (Other colorants) The colorant (A) may contain other colorants in addition to the pigment (A1) represented by the general formula (1) and the yellow pigment (A3). Red pigments include, for example, CI 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 ,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,1 79,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,2 No. 59,260,262,263,264,265,266,267,268,269,270,271,273,274,275,276,277,278,279,280,281,282,283,284,285,286,287,291,295,296, and JP-A-2014-134712. Also included are the pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844 are more preferred.

[0029] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0030] 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, sulfur dyes, etc. In addition, examples of the dye include dye derivatives and lake pigments obtained by converting dyes into lakes.

[0031] The dye is preferably used as a salt-forming compound. Examples of the salt-forming compound include a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound of a resin component having an amino group and an acid dye; a salt-forming compound of an acid dye and a compound having an onium base; a salt-forming compound of a basic dye and an organic acid, perchloric acid, or a metal salt thereof. Among these, the salt-forming compound of a basic dye is preferred because it has excellent resistance to various types of substances and compatibility with pigments. The compound having an onium base is preferably a resin having a cationic group in the side chain.

[0032] The chemical structure of the dye may be, for example, an azo dye, a disazo dye, an azomethine dye (such as an indoaniline dye or an indophenol dye), a dipyrromethene dye, a quinone dye (such as a benzoquinone dye, a naphthoquinone dye, anthraquinone dye, or anthrapyridone dye), a carbonium dye (such as a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, or an acridine dye), a quinoneimine dye (such as an oxazine dye), or a quinoneimine dye (such as an oxazine dye). 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, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color properties 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.

[0033] Other preferred colorants include CI Pigment Red 177, 254, 291, 295, and 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844.

[0034] <Mixing pigments> Among colorants, organic pigments are preferably mixed with other raw materials after being subjected to a micronization treatment. Examples of the method of micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0035] During the salt milling treatment, a resin can be added as necessary. 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 and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0036] <Metal Removal> If a specific metal element is present in a large amount in the photosensitive coloring composition as an impurity other than the pigment constituent, it inhibits dispersion stability over time. In addition, it may cause a decrease in heat resistance or a decrease in sensitivity. In addition, a color filter made using this may have foreign matter, which may result in a decrease in brightness. 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 preferably 500 mass ppm or less.

[0037] The total amount of the specific metal elements is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more. Within the above range, the photosensitive coloring composition can be obtained that can suppress costs, has excellent storage stability, and can form a color filter with little generation of foreign matter and little decrease in brightness.

[0038] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0039] In addition, since it is desired to suppress impurities that do not constitute the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, which constitute the pigment, they can be removed in the same manner as the specific metal elements, for example, by the following method. Furthermore, Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (for example, catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, so they are removed as much as possible.

[0040] Methods for removing the colorant (A) or metals that have become mixed in from equipment during the manufacturing process include the water washing methods described in JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and the method of removing magnetic foreign matter using a magnet described in JP-A-2011-48736.

[0041] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0042] <Dye derivatives> The photosensitive coloring composition may use a dye derivative as necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl 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, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0043] The dye derivatives can be used alone or in combination of two or more kinds.

[0044] The content of the dye derivative is preferably from 1 to 100 parts by mass, more preferably from 3 to 70 parts by mass, and even more preferably from 5 to 50 parts by mass, relative to 100 parts by mass of the pigment.

[0045] When a dye derivative is added to a pigment and a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling is performed, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0046] <Resin-type dispersant (B)> The resin type dispersant (B) is not particularly limited as long as it can disperse the colorant (A), but in this specification, a resin type dispersant having an aromatic carboxylic acid moiety is preferred. The aromatic carboxylic acid moiety has an aromatic ring that has a high affinity with the surface and a carboxyl group that is directly bonded to the aromatic ring. In addition, the resin type dispersant (B) preferably has a steric repulsion moiety to enhance dispersibility.

[0047] Examples of the resin type dispersant (B) include a resin type dispersant (B1) having an aromatic carboxylic acid moiety and a vinyl polymer moiety (hereinafter referred to as resin type dispersant (B1)), and a resin type dispersant (B2) having an aromatic carboxylic acid moiety and a lactone residue moiety (hereinafter referred to as resin type dispersant (B2)). Among these, the resin type dispersant (B1) is preferred. The vinyl polymer moiety is a steric repulsion moiety and can contain a (meth)acryloyl group or a thermal crosslinking group. This provides photocrosslinkability or thermal crosslinkability. The lactone residue moiety is also a steric repulsion moiety. The aromatic carboxylic acid moiety in the resin-type dispersant (B) with aromatic carboxylic acid moiety has a high affinity with the pigment surface, so it efficiently wraps around the pigment. This reduces the exposed surface area of ​​the pigment, making it less likely for the substrate and the pigment to come into direct contact, improving adhesion. In addition, the aromatic ring in the said moiety has a π-electron conjugated unsaturated ring structure that has a high absorption of ultraviolet light with a wavelength of 250 nm or less, and it is speculated that the rectangularity is improved by suppressing the spread of ultraviolet light from the edge of the photomask.

[0048] <Resin-type dispersant (B1)> The resin-type dispersant (B1) is, for example, a resin-type dispersant described in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, JP1996-143651A, JP2007-140487A, or the like.

[0049] The aromatic carboxylic acid moiety is, for example, a compound derived from one or more acid anhydrides selected from tetracarboxylic acid anhydrides or tricarboxylic acid anhydrides.

[0050] The acid value of the resin-type dispersant (B1) is preferably from 10 to 250 mgKOH / g, more preferably from 40 to 200 mgKOH / g, and even more preferably from 50 to 160 mgKOH / g. A suitable acid value improves storage stability.

[0051] (Side chain that is a vinyl polymer moiety) The side chain of the resin type dispersant (B1) is synthesized by polymerizing a monomer in the presence of a compound having a thiol group. The compound having a thiol group is preferably a compound having two hydroxyl groups and one thiol group in the molecule. The resin type dispersant (B1) can be synthesized by a method of forming an aromatic carboxylic acid moiety after synthesizing a side chain that is a vinyl polymer moiety, or by a method of forming an aromatic carboxylic acid moiety after synthesizing a side chain that is a vinyl polymer moiety. In the former method, a vinyl polymer having two hydroxyl groups near one end can be formed. In the latter method, a compound having two hydroxyl groups and one thiol group in the molecule is used to synthesize an aromatic carboxylic acid moiety, and then a monomer is added and polymerized to form a vinyl polymer starting from the thiol group of the compound having two hydroxyl groups and one thiol group in the molecule.

[0052] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0053] The Tg of the vinyl polymer portion of the resin-type dispersant (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 more excellent high-definition fine pixel pattern can be formed. The upper limit of Tg is preferably 100°C.

[0054] The weight average molecular weight of the vinyl polymer portion of the resin-type dispersant (B1) is preferably from 500 to 30,000, more preferably from 5,000 to 20,000, and even more preferably from 7,000 to 10,000.

[0055] The number average molecular weight of the vinyl polymer portion of the resin-type dispersant (B1) is preferably 2,000 to 6,000.

[0056] The vinyl polymer moiety of the resin-type dispersant (B1) preferably has one or more functional groups selected from the group consisting of a (meth)acryloyl group and a thermally crosslinkable group, which enhances the degree of crosslinking of the coating film by a pulse exposure step of ultraviolet light having a wavelength of 250 nm or less and a subsequent heating step.

[0057] Examples of resin-type dispersants having a (meth)acryloyl group in a vinyl polymer moiety include the moiety described in JP 2011-157416 A. For example, a moiety obtained by reacting a hydroxyl group in a vinyl polymer moiety obtained by radical polymerization of an ethylenically unsaturated monomer having no hydroxyl group and an ethylenically unsaturated monomer having a hydroxyl group with an isocyanate group in a compound having one isocyanate group and one or more (meth)acryloyl groups can be mentioned.

[0058] An example of a resin-type dispersant having a thermally crosslinkable group in a vinyl polymer moiety is the dispersant described in JP 2009-155406 A. For example, the vinyl polymer moiety can be formed using at least one monomer selected from a blocked isocyanate group-containing monomer, an oxetane group-containing monomer, and a tert-butyl group-containing monomer.

[0059] Other monomers that can be used in the synthesis of the vinyl polymer portion include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0060] Resin-type dispersants (B1) can be classified according to their molecular structure into comb-shaped and straight-chain resin-type dispersants. Of these, comb-shaped resin-type dispersants are preferred.

[0061] The comb-shaped resin-type dispersant 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. Examples of the tetracarboxylic acid anhydride, which is the raw material for the comb-shaped resin-type dispersant, and the raw material for the vinyl polymer, which is a part of the structure, include compounds described in WO2008 / 007776.

[0062] The tetracarboxylic acid anhydride used in the present invention is a compound having two carboxylic acid anhydride groups. In this specification, aromatic tetracarboxylic acid dianhydrides are preferred from the viewpoint of reducing the viscosity of the photosensitive coloring composition. Examples of aromatic tetracarboxylic acid dianhydrides include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic acid dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 1,4,5,8 ... Carboxylic acid dianhydrides, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride , 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride. Among these, pyromellitic anhydride is preferred.

[0063] For example, a straight-chain resin-type dispersant 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 anhydride. Examples of the straight-chain resin-type dispersant include the compounds described in JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651.

[0064] Examples of tricarboxylic anhydrides include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, 3,4,4'-biphenylsulfonetricarboxylic anhydride, etc. Among these, trimellitic anhydride is preferred.

[0065] <Resin-type dispersant (B1-R)> In this specification, the resin-type dispersant (B1-R) is a dispersant synthesized based on the comb-shaped resin-type dispersant (B1). It has a main chain containing an aromatic carboxylic acid ester moiety having an ester bond formed by esterification reaction of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety, and the amount of the acid anhydride groups relative to 1 mole of the hydroxyl groups is preferably 0.9 to 1.5 moles, more preferably 1.0 to 1.3 moles. Furthermore, the main chain containing the aromatic carboxylate moiety has a terminal blocking moiety derived from a terminal blocking material (e.g., monoalcohol, monoamine), that is, during the esterification reaction, the acid anhydride group reacts with the terminal blocking material to generate an alcohol ester group (or amide group) and a carboxyl group. The use of the resin-type dispersant (B1-R) improves the filterability of the photosensitive coloring composition, and can suppress the formation of foreign matter on the coating film formed by coating the photosensitive coloring composition. In addition, when the photosensitive coloring composition is coated, for example, with a die coater, a solidified material originating from the photosensitive coloring composition is formed on the coater head. However, the use of the resin-type dispersant (B1-R) improves the resolubility of the solidified material in propylene glycol monomethyl ether acetate, and can suppress the formation of foreign matter on the coating film. In the present invention, the side chain based on the vinyl polymer moiety is formed by polymerization of an ethylenically unsaturated monomer. Note that the total monomer units constituting the vinyl polymer moiety refer to partial structures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0066] (Monoalcohol) Examples of monoalcohols include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; Examples of the monoalcohols include monoalcohols having an ether group such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; and monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, and diacetone alcohol. These may be used alone or in combination of two or more.

[0067] The monoalcohol is preferably 3-methoxybutanol, propylene glycol monomethyl ether, or diacetone alcohol, which is a compound having an ether group or a carbonyl group. This gives the dispersant an ether group or a carbonyl group near the end of the main chain, making it easier to redissolve in the organic solvent propylene glycol monomethyl ether acetate (PGMAc).

[0068] The main chain which is an aromatic carboxylate moiety may have a blocking moiety which is reacted with water, in addition to a blocking moiety derived from a monoalcohol.

[0069] From the viewpoint of reaction control, the monoamine is preferably a secondary amine. By using a secondary amine, side reactions such as a crosslinking reaction with an aromatic compound having two or more acid anhydride groups can be suppressed. Examples of secondary amines include aliphatic secondary amines such as dimethylamine, diethylamine, ethylmethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-s-butylamine, di-tert-butylamine, N-methylbutylamine, N-ethylbutylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-2-ethylhexylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine (dilaurylamine), di-n-tridecylamine, di-n-tetradecylamine (dimyristylamine), di-n-hexadecylamine (dipalmitylamine), di-n-stearylamine, and diisostearylamine; Alicyclic secondary amines such as N-methylcyclopentylamine, N-ethylcyclopentylamine, N-propylcyclopentylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, and N-isopropylcyclohexylamine; Examples of the aromatic secondary amines include N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine, N-isopropylbenzylamine, N-butylbenzylamine, 1-(methylaminomethyl)naphthalene, and 9-(methylamino)methylanthracene. These may be used alone or in combination.

[0070] The end-capping agent is preferably a monoalcohol. This makes it easier to control the reaction during synthesis of the polyester dispersant. It also improves dispersibility and PGMAc resolubility.

[0071] Regarding the synthesis of the capping portion, the amount of the terminal capping agent used relative to the acid anhydride group is preferably 1 to 30 molar equivalents relative to 1 equivalent of the acid anhydride group remaining in the main chain, and more preferably 1.5 to 20 molar equivalents. When the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability, and when the amount is 30 molar equivalents or less, ester exchange reaction due to the ester bond between the monoalcohol and the dispersant is unlikely to occur, and a decrease in molecular weight is unlikely to occur.

[0072] <Resin-type dispersant (B2)> The resin-type dispersant (B2) having an aromatic carboxylic acid compound residue and a polylactone side chain is a resin represented by the following general formula (7), and its materials and synthesis method are described, for example, in JP-A-2007-140487. General formula (7) (HOOC-) m -R 1 -(-COO-[-R 3 -COO-] n -R 2 ) t (In the formula, R 1 is a tetravalent aromatic tetracarboxylic acid compound residue, R 2 is a monoalcohol residue, R 3 represents a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4-m).

[0073] The resin represented by the above general formula (7) has both a tetravalent tetracarboxylic acid compound residue and a lactone residue. This makes it easy to achieve both excellent stability of the photosensitive coloring composition and strong adhesion between the coating film and a transparent substrate such as glass. The synthesis method of the resin represented by the general formula (7) is not limited, but for example, it is preferable to carry out a first step of synthesizing a polylactone having a hydroxyl group at one end by ring-opening polymerization of a lactone using a monoalcohol as an initiator, and a second step of reacting the polylactone having a hydroxyl group at one end with a tetracarboxylic acid anhydride.

[0074] Examples of monoalcohols include methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octanol, 1 ... Aliphatic monoalcohols such as ethyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, and oleyl alcohol; aromatic monoalcohols such as benzyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono-2-ethylhexyl ether,Examples of alkylene glycol monoalkyl ethers include tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene glycol monomethyl ether.

[0075] Polylactones having a hydroxyl group at one end can be synthesized by ring-opening polymerization of lactones using monoalcohol as an initiator. Examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone. Among these, δ-valerolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone are preferred in terms of ring-opening polymerization properties.

[0076] (Other resin-type dispersants) The photosensitive coloring composition can contain an acidic resin type dispersant and a basic resin type dispersant other than the resin type dispersant (B1) and (B2). Examples of the acidic resin type dispersant include urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and their modified products, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and their salts, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0077] Examples of basic resin-type dispersants include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, and the like.

[0078] The content of the resin-type dispersant (B) is preferably about 3 to 200% by mass, and more preferably about 5 to 100% by mass, based on the colorant (A). When an appropriate amount is contained, the film-forming property is further improved.

[0079] <Binder resin (C)> The binder resin (C) is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. The binder resin (C) is preferably a thermoplastic resin or a photosensitive resin. The binder resin (C) is preferably alkali-soluble. This allows the coating formed from the photosensitive coloring composition to be patterned by a photolithography method. The photosensitive resin not having alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group. The binder resin is preferably a random polymer of a monomer. The random polymer is preferably a chain (including a branched chain).

[0080] The binder resin (C) can be used alone or in combination of two or more kinds.

[0081] The content of the binder resin (C) is preferably 1 to 200 parts by mass, more preferably 2 to 100 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0082] Examples of the alkali-soluble resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0083] <Thermoplastic resin> Thermoplastic resins are not alkali-soluble. Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes (HDPE, LDPE), polybutadiene, and polyimide resins.

[0084] <Alkali-soluble photosensitive resin> The alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group. Any known resin can be used as the alkali-soluble photosensitive resin as long as it is alkali-soluble and photosensitive, but a resin synthesized by the following method (i) or (ii) is preferred. When an alkali-soluble photosensitive resin is used, it is three-dimensionally crosslinked by light irradiation, increasing the crosslink density, improving the chemical resistance of the coating.

[0085] [Method (i)] Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0086] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0087] Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro or cyano at the α-position.

[0088] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride group.

[0089] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0090] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-phenylenediamine benzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0091] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0092] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0093] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0094] Monomers that can be used other than the above-mentioned monomers include, in addition to the other monomers exemplified in the above method (i), phosphate ester group-containing monomers, etc.

[0095] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0096] The above-mentioned monomers of the binder resin (C) can be used alone or in combination of two or more kinds. The binder resin (C) can be used alone or in combination of two or more kinds.

[0097] The weight average molecular weight (Mw) of the binder resin (C) is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000. The value of Mw / Mn is preferably not more than 10. Here, Mn is the number average molecular weight.

[0098] The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 80 to 170 mgKOH / g. A suitable acid value allows a high level of balance to be achieved among alkali solubility, adhesion, and residue suppression.

[0099] <Thermosetting compounds> The photosensitive coloring composition can contain a thermosetting compound. When a color filter is produced using the photosensitive coloring composition, the thermosetting compound is thermally cured in the post-baking process to increase the crosslink density of the coating, thereby improving heat resistance. This suppresses pigment aggregation in the post-baking process, improving the contrast ratio.

[0100] Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0101] Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene ... Examples of the epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

[0102] (Oxetane Compounds) The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0103] Examples of monofunctional oxetane compounds include (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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0104] Examples of bifunctional oxetane compounds include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, ... -Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-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 bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like.

[0105] The trifunctional or higher oxetane compounds are 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, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol 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., the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0106] The content of the thermosetting compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the solvent resistance of the coating film is further improved.

[0107] <Polymerizable compound (D)> The polymerizable compound (D) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (D) include hydroxyl group-containing monomers, acid group-containing monomers, urethane bond-containing monomers, and other monomers. Among these, the polymerizable compound (D) is preferably a compound (D1) represented by general formula (3). The polymerizable unsaturated group is, for example, a vinyl group, a (meth)acryloyl group, a (meth)allyl group, and the like. The oligomer is a compound having a molecular weight of 1000 or more.

[0108] (Polymerizable compound having a hydroxyl group) The polymerizable compound having a hydroxyl group is preferably a compound (D1) represented by general formula (3). The coating containing the compound (D1) represented by general formula (3) has increased solubility in an alkaline developer due to the action of the hydroxyl group, and can suppress development residues. In addition, the presence of the hydroxyl group results in a highly polar hydrophilic site in the coating, making it difficult for non-polar oxygen molecules to coexist. This makes it difficult for polymerization inhibition due to oxygen to occur during exposure, making it easier to create a pattern with high rectangularity. General formula (3) [ka]

[0109] In the formula (3), X is a partial structure represented by the following formula (4), (5), or (6). 1 , R 2 represents a hydrogen atom or a methyl group. [ka]

[0110] In formula (4), n represents an integer of 1 to 4; 3 represents a hydrogen atom or a methyl group. In formula (5), n represents an integer of 1 to 4. In formula (6), n represents an integer of 1 to 4.

[0111] Examples of the compound (D1) represented by the general formula (3) include ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, triethylene glycol diglycidyl ether di(meth)acrylate, tetraethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di(meth)acrylate, dipropylene glycol diglycidyl ether di(meth)acrylate, tripropylene ... Examples of suitable diglycidyl ether di(meth)acrylate include tertiary propylene glycol diglycidyl ether di(meth)acrylate, 1,3-propanediol diglycidyl ether di(meth)acrylate, 1,4-butanediol diglycidyl ether di(meth)acrylate, glycerin diglycidyl ether di(meth)acrylate, diglycerin diglycidyl ether di(meth)acrylate, triglycerin diglycidyl ether di(meth)acrylate, and tetraglycerin diglycidyl ether di(meth)acrylate. Among these, propylene glycol diglycidyl diacrylate is more preferred in terms of the polymerizable unsaturated group equivalent and the distance between the polymerizable unsaturated groups, and glycerin diglycidyl ether diacrylate is more preferred in terms of the hydroxyl group equivalent. Both of these contribute to improved curing properties, making it easier to produce a highly rectangular pattern.

[0112] The content of the compound (D1) represented by the general formula (3) is preferably from 1 to 50 mass %, and more preferably from 2 to 40 mass %, in 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0113] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

[0114] Examples of the acid group-containing monomer include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0115] (Urethane bond-containing monomer) Examples of the urethane bond-containing monomer include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0116] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0117] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0118] 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, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include 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, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0119] The polymerizable compound (D) can be used alone or in combination of two or more kinds.

[0120] The blending amount of the polymerizable compound (D) is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0121] <Photopolymerization initiator (E)> As the photopolymerization initiator (E), various photopolymerization initiators can be used, but in this specification, oxime ester-based photopolymerization initiators are preferred. In oxime ester photopolymerization initiators, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, which allows patterns to be formed with less exposure compared to when other photopolymerization initiators are used, improving photocuring properties.

[0122] Examples of the oxime ester photopolymerization initiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF Japan Ltd.), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, and TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA OPTOMER N-1919, ADEKA ARCLES NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

[0123] Oxime ester photopolymerization initiators can be classified according to their molecular skeleton, and include carbazole skeletons, fluorene skeletons, diphenyl skeletons, and dioxime-based initiators having two oxime ester groups. The specific structure of the oxime ester photopolymerization initiator is preferably, for example, a hydroxyl group, a nitro group, a carbonyl group, a fluorocarbon group, or a benzofuran group.

[0124] (Oxime ester photopolymerization initiator having a carbazole skeleton) [ka] JPEG2025037336000012.jpg105149

[0125] (Fluorene skeleton-containing oxime ester photoinitiator) [ka]

[0126] (Oxime ester photoinitiator with diphenyl skeleton) [ka]

[0127] (Photopolymerization initiator with two oxime ester groups) As shown below, examples of the photopolymerization initiator include a photopolymerization initiator having two oxime ester groups on both sides of a carbazole skeleton or a phenothiazine skeleton. [ka]

[0128] The photopolymerization initiator (E) preferably contains one or more oxime ester compounds selected from the group consisting of the following (E1), (E2) and (E3) among the oxime ester photopolymerization initiators described above. The use of these oxime ester compounds further improves rectangularity and adhesion. (E1) Compound having two oxime ester groups and a carbazole skeleton (E2) Compounds having two oxime ester groups and a phenothiazine skeleton (E3) A compound represented by the following general formula (2): General formula (2) [ka]

[0129] In general formula (2), R 2 R represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 3 R represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. 4 R represents a branched alkyl group or a cyclic organic group having 6 or more carbon atoms. 5 represents a monovalent substituent (excluding an oxime ester group), and n represents an integer of 0 to 3.

[0130] (E1) Examples of the compound having two oxime ester groups and a carbazole skeleton are shown below. [ka]

[0131] (E2) Examples of compounds having two oxime ester groups and a phenothiazine skeleton are shown below. [ka]

[0132] Examples of the compound represented by formula (2) are shown below. [ka] JPEG2025037336000020.jpg93124

[0133] As the photopolymerization initiator (E), a polymerization initiator other than the oxime ester-based photopolymerization initiator can be used. Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- butylperoxycarbonyl)benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone and other thioxanthone compounds; 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( triazine-based compounds such as 2-(naphth-1-yl)-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 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of the compounds include phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

[0134] The content of the photopolymerization initiator (E) is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the nonvolatile content of the photosensitive composition. When an appropriate amount is added, the photocurability and developer resistance are improved, and the surface condition of the coating film tends to become smooth.

[0135] <Sensitizer> The photosensitive coloring composition may further contain a sensitizer. Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and 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, and 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's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, 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. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, and the like are more preferred.

[0136] The sensitizers can be used alone or in combination of two or more kinds.

[0137] The content of the sensitizer is preferably from 3 to 60 parts by mass, and more preferably from 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (E). When an appropriate amount is contained, the curability and developability are further improved.

[0138] <Thiol-based chain transfer agents> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, and the sensitivity of the photosensitive coloring composition is improved.

[0139] The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

[0140] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, and ethylene glycol bisthiopropionate. Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0141] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0142] The content of the thiol chain transfer agent is preferably 0.1 to 10 mass%, more preferably 0.1 to 3 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0143] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

[0144] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl Examples of the alkyl resorcinol compounds include alkyl resorcinol compounds such as n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

[0145] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, a good pattern shape is easily obtained.

[0146] <Ultraviolet absorbing agent> The photosensitive coloring composition may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorbing agent may be an oligomer or a polymer.

[0147] The content of the ultraviolet absorber is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0148] 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 an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0149] Benzotriazole compounds include, for example, 2-(5-methyl-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-methylphenyl Mixture of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain alkyl esters with 95% methoxy-1-methylethyl acetate, 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 products, 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, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0150] Examples of 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-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-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, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0151] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0152] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0153] <Antioxidants> The photosensitive coloring composition can contain an antioxidant. The antioxidant can prevent the coating film formed from the photosensitive coloring composition from yellowing due to oxidation during the thermal process of heat curing or ITO annealing, and suppress the decrease in the transmittance of the coating film. In particular, when the pigment concentration of the photosensitive coloring composition is high, the content of the polymerizable compound (D) is relatively reduced, so that the coating film is likely to yellow when the amount of the photopolymerization initiator is increased or a thermosetting compound is blended. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and the decrease in the transmittance of the coating film can be suppressed.

[0154] The antioxidant is a compound having a radical scavenging function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. The antioxidant is preferably a compound that does not contain a halogen atom.

[0155] Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0156] The antioxidants can be used alone or in combination of two or more kinds.

[0157] The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition, since the transmittance, spectral characteristics, and sensitivity are excellent.

[0158] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the transparent substrate during film formation and the drying property of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0159] The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the non-volatile content of the photosensitive coloring composition. By being within this range, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0160] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0161] The content of the storage stabilizer is preferably 0.1 to 10% by mass based on 100 parts by mass of the colorant (A).

[0162] <Adhesion improver> The photosensitive coloring composition may contain an adhesion improver. This improves the adhesion between the substrate and the coating. Examples of the adhesion improver include a silane coupling agent. Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2-( aminosilanes such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0163] The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, the adhesion of the coating is further improved, and the resolution of the pattern is also further improved.

[0164] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a coating with a smooth surface. The solvent may be appropriately selected according to the purpose of use, and may be contained in an appropriate amount.

[0165] Examples of the solvent include ester solvents (solvents containing -COO- but not -O- in the molecule), 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 and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0166] Among these, in terms of coatability and drying property, solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferred. For example, 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, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

[0167] The solvents can be used alone or in combination of two or more.

[0168] <Method for producing photosensitive coloring composition> The photosensitive coloring composition is prepared by dispersing a pigment dispersion using, for example, a colorant (A), a resin-type dispersant (B), a solvent, etc. Then, the pigment dispersion, a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E) are mixed together to prepare the photosensitive coloring composition. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

[0169] The dispersion treatment can be carried out using a dispersion device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0170] <Removal of large particles> The photosensitive coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the photosensitive coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is preferable that the particles are 0.3 μm or less.

[0171] <Water content in photosensitive coloring composition> The photosensitive coloring composition of the present invention preferably has a water content of 2 mass % or less.

[0172] When the water content is set to the above, the photosensitive coloring composition has excellent dispersion stability and sensitivity even after storage over time. The water content 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 low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0173] The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method for producing a photosensitive coloring composition while blowing in a dry inert gas, or a method for dehydrating the composition by adding molecular sieves after production, etc. can be mentioned. Among them, the method for producing the composition while blowing in a dry inert gas is preferred.

[0174] The water content can be measured by a known method such as the Karl Fischer method.

[0175] <Amount of toluene in the photosensitive coloring composition> The photosensitive coloring composition of the present invention may contain toluene. The content of toluene in the photosensitive coloring composition is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0176] <Color filters> The color filter of the present invention has filter segments (also called pixels) formed from a photosensitive coloring composition. The color filter preferably has a base material (substrate). The filter segments preferably have red filter segments, green filter segments, and blue filter segments by appropriately selecting the type of colorant (A) used. The filter segments may have magenta filter segments, cyan filter segments, and yellow filter segments instead of these. A reflective substrate may 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.

[0177] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0178] The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferred method is the photolithography method.

[0179] In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a coating. The obtained coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the coating is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, thereby further improving the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0180] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0181] <Exposure process> For the exposure, pulsed exposure to ultraviolet light with a wavelength of 250 nm or less is used for pattern formation. For the exposure, ultraviolet light with a wavelength of 180 nm or more is preferred. Examples of the wavelength of the exposure include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). KrF rays (wavelength 248 nm) are preferred because the bonds of the coloring materials contained in the photosensitive coloring composition are less likely to be broken. In addition, the exposure device is preferably a KrF ray scanner exposure device. According to this embodiment, the alignment accuracy of the exposure is good, and fine pixels can be easily formed. Examples of the light source include an excimer laser light source and a far ultraviolet lamp. An excimer laser light source is preferred because it can be exposed to high-intensity light instantaneously, which is advantageous for curing properties.

[0182] In addition, although there is a method of continuously irradiating light during exposure, pulse (intermittent) exposure is used because it is easier to obtain better curing properties. The pulse exposure is an exposure method in which light irradiation and pause are repeated in a short cycle (for example, millisecond level or less). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less, because it is easy to generate a large amount of active species such as radicals instantaneously. There is no particular limit to the lower limit of the pulse width, but it can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more, because it is easy to promote thermal polymerization due to exposure heat. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less, because it is easy to suppress deformation of the substrate due to exposure heat. The maximum instantaneous irradiance is 50,000,000 W / m from the viewpoint of curing. 2 More preferably, it is 100,000,000 W / m 2 More preferably, it is 200,000,000 W / m or more. 2 It is more preferable that the upper limit of the maximum instantaneous illuminance is 1000000000 W / m from the viewpoint of suppressing high illuminance failure. 2 Preferably, it is less than 800,000,000 W / m 2 More preferably, it is 500,000,000 W / m or less. 2 It is more preferable that the pulse width is equal to or less than 1000 s. The pulse width refers to the time during which light is irradiated in a pulse period. The frequency refers to the number of pulse periods per second. The maximum instantaneous irradiance refers to the average irradiance during the time during which light is irradiated in a pulse period. The pulse period refers to a period in which light irradiation and pause in pulse exposure constitute one cycle.

[0183] The exposure dose is, for example, 1 to 2000 mJ / cm 2 The upper limit is 1000 mJ / cm 2Less than 500 mJ / cm is preferable. 2 The lower limit is 5 mJ / cm. 2 More than 10 mJ / cm is preferable. 2 More preferably, 20 mJ / cm or more. 2 The above is even more preferable.

[0184] The oxygen concentration during exposure can be appropriately selected. In addition to being performed in air, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, 50 volume%).

[0185] The exposure equipment used for pulse exposure is preferably a reduction projection exposure equipment. Reduction projection exposure equipment includes a step-and-repeat type (step-per), which exposes a square area with one light irradiation (one shot), and a step-and-scan type (scanner), which exposes by irradiating light while moving (scanning) a long, thin slit-shaped area in the horizontal direction.

[0186] A stepper exposes the roughly circular exposure area defined by the optical lens for reduction projection exposure by dividing it into squares and performing one-shot exposure, so it is affected by lens distortion, whereas a scanner defines the exposure area in the center of the optical lens for reduction projection exposure as a slit, and scans and exposes the slit. For this reason, compared to a stepper, a scanner uses only the area of ​​the lens with less distortion for exposure. Exposing an area with less distortion improves the printing accuracy (overlay accuracy, etc.) of the pattern formed on the reticle onto the wafer substrate.

[0187] The developer may be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine, triethanolamine, or TMAH (tetramethylammonium hydroxide). An antifoaming agent or a surfactant may be added to the developer.

[0188] The color filter of the present invention is laminated to an opposing 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 laminated to the outside of the substrate as necessary, to produce a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0189] The color filter in this specification can be used for applications such as solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays, in addition to liquid crystal displays.

[0190] <Solid-state imaging element> The solid-state imaging device of the present invention includes the above-mentioned color filter of the present invention. The solid-state imaging device is not particularly limited, but examples thereof include the following configurations.

[0191] The solid-state imaging element has, on a support, a plurality of photodiodes constituting a light receiving area thereof and a transfer electrode made of polysilicon or the like; a light-shielding film made of tungsten or the like is provided on the photodiodes and the transfer electrode, with only the light receiving portions of the photodiodes being opened; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portions of the photodiodes; and a cured film of the present invention is provided on the device protection film. Furthermore, the device protective film may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided below the cured film of the present invention (on the side closer to the support), or a configuration in which a focusing means is provided on the cured film of the present invention. In addition, in the solid-state imaging device, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partition walls, for example in a lattice shape. In this case, it is preferable that the partition walls have a low refractive index with respect to each color pixel.

[0192] <Liquid crystal display device> The liquid crystal display device of the present invention includes a color filter. The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because it widens the red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Fig. 1 comprises a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and a liquid crystal LC is sealed between them.

[0193] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), etc. 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. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0194] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0195] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0196] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0197] The white LED light source may be one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a fluorescent material is contained in the resin package of a blue LED, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. In particular, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0198] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0199] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.). EXAMPLES

[0200] The present invention will be described below with reference to examples. However, the present invention is not limited to the examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass".

[0201] Prior to the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0202] <Average primary particle size of pigment> The average primary particle size of the pigment was measured by a common method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis and major axis diameters of each pigment primary particle were measured, and the average was taken as the particle size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

[0203] (Dispersed particle size measurement) Using Nikkiso's Microtrac UPA-EX150 with dynamic light scattering (FFT power spectrum method), particle transmittance was set to absorption mode, particle shape was set to non-spherical, and D50 was set to average diameter. The same solvents used for the dispersion were used as dilution solvents for the measurement, and the samples treated with ultrasonic waves were measured immediately after sample preparation.

[0204] (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. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalent values.

[0205] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) of the resin solution was measured. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0206] (Amine value (mgKOH / g) of basic resin type dispersant) The amine value of a basic resin type dispersant is a value obtained by converting the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 into non-volatile content.

[0207] (Ammonium salt value (mgKOH / g)) The ammonium salt value is determined by titrating with 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then converted to the potassium hydroxide equivalent, and indicates the ammonium salt value of the non-volatile content.

[0208] <Method of manufacturing fine pigment> (Production of Micronized Pigment (A1-1)) 100 parts of CI Pigment Red 272 represented by formula (a1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80° C. to form a slurry, which was then filtered and washed with water to remove the salt and diethylene glycol, and then dried overnight at 80° C. and pulverized to obtain a finely divided pigment (A1-1) having a diketopyrrolopyrrole pigment.

[0209] (Production of Micronized Pigments (A1-2) to (A1-9)) The fine pigments (A1-2) to (A1-9) were obtained in the same manner as in the production of the fine pigment (A1-1), except that the CI Pigment Red 272 represented by formula (1) was changed to the pigments represented by formulas (a1-2) to (a1-9).

[0210] (Production of finely divided pigment (A2-1)) A diketopyrrolopyrrole-based fine pigment (A2-1) was obtained in the same manner as in the production of the fine pigment (A1-1), except that CI Pigment Red 272 was changed to CI Pigment Red 254 (BASF Japan Ltd.'s "Irgaphor Red B-CF").

[0211] (Micronized pigment (A3-1)) 100 parts of CI Pigment Yellow 139 (BASF Japan "Irgaphor Yellow 2R-CF"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded mixture was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain a fine pigment (A3-1).

[0212] (Production of Micronized Pigments (A3-2) to (A3-4)) Quinophthalone pigment fine particles (A3-2) to (A3-4) were prepared according to the examples in JP 2012-226110 A. Their structures are shown below.

[0213] [ka]

[0214] (Micronized pigment (A3-5)) 100 parts of a metal complex yellow pigment (CI Pigment Yellow 150, Lanxess "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 10 hours at 60° C. 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, which was filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for one day and night to obtain a finely divided yellow pigment (A3-5).

[0215] (Micronized pigment (A3-6)) The azobarbituric acid precursor was prepared according to the synthesis method described in JP 2017-171915 A. (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 about pH 5 with aqueous potassium hydroxide solution and stirring was continued for 90 minutes. Azobarbituric acid (0.3 moles) 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. After that, 79.4 parts of melamine (0.63 moles) were added. Then, a mixed solution of 0.225 moles of 25% nickel chloride + 0.075 moles of 25% zinc chloride was added dropwise. After 3 hours at 82°C, the pH was adjusted to about 5.5 using an aqueous potassium hydroxide solution. This was followed by dilution with about 100 parts of distilled water at 90°C. Then, 21 parts of 30% hydrochloric acid were added dropwise and the temperature was kept at 90°C for 12 hours. Then, the pH was adjusted to about 5 using an aqueous potassium hydroxide solution. The pigment was then isolated on a suction filter, washed, dried at 80° C. in a vacuum drying cabinet, and ground for 2 minutes in a standard laboratory mill to obtain the melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with a composition of 25 mol % Zn and 75 mol % Nickel. 100 parts of the hybrid compound, 10 parts of the dye derivative (d-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. 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, which was filtered and washed repeatedly to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain a finely-processed metal azo pigment (A3-6). General formula (8) [ka] (In the general formula (8), Me represents Ni or Zn.)

[0216] (Micronized pigment (A3-7)) 50 parts of CI Pigment Yellow 185 (BASF Japan "Paliotol Yellow L 1155"), 250 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 100° C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. overnight to obtain a finely divided pigment (A3-7).

[0217] Table 1 shows the average primary particle size (nm) of each finely divided pigment.

[0218] [Table 1]

[0219] <Dye manufacturing method> (Resin 1 having cationic groups on the side chains) A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated 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, 6.5 parts of 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-necked separable flask, and reacted while dropping for 2 hours. After the end of the dropwise addition, the reaction was continued for 2 hours. The nonvolatile content was measured to confirm that the polymerization yield was 98% or more 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 the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, resin 1 having cationic groups on the side chains having ammonium groups and a resin component of 47% by mass was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

[0220] (Dye 01(AR52-JK)) Dye 01 (AR52-JK), which is a salt-forming compound consisting of CI Acid Red 52 and Resin 1 having a cationic group on the side chain, was produced according to the following procedure. 30 parts of the resin 1 having a cationic group on the side chain was added to 2000 parts of water in terms of non-volatile content, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and the solution was gradually added to the resin solution. After the addition, the mixture was stirred at 60°C for 120 minutes to thoroughly 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 when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, the mixture was filtered by suction, washed with water, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain dye 01 (AR52-JK), which is a salt-forming compound of 32 parts of CI Acid Red 52 and resin 1 having a cationic group on the side chain. At this time, the content of the active color component derived from CI Acid Red 52 in dye 01 (AR52-JK) was 25% by mass.

[0221] <Method of manufacturing dye solution> (Dye solution (DS-01)) The following mixture was stirred and mixed until homogeneous, 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

[0222] <Production of fine pigments for producing green and blue color filters>

[0223] (Micronized pigment (A4-1)) 100 parts of phthalocyanine green pigment CI Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded mixture was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. overnight to obtain a finely divided pigment (A4-1).

[0224] (Micronized pigment (A4-2)) 100 parts of blue pigment CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A4-2).

[0225] (Micronized pigment (A4-3)) 100 parts of purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 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, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain a finely divided pigment (A4-3).

[0226] <Basic dye derivatives> The following basic dye derivatives were used: Basic Dye Derivatives (1) [ka] Basic Dye Derivatives (2) [ka]

[0227] (Manufacture of resin-type dispersants) (Production example of dispersant (B1-R-1: comb-shaped)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added to 6.0 parts of 3-mercapto-1,2-propanediol, and the reaction was carried out for 10 hours. It was confirmed by measuring the non-volatile content that more than 95% of the monomer had reacted. Next, 14.5 parts of pyromellitic dianhydride, 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C. for 5 hours. By measuring the amount of remaining acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Then, 12.1 parts of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C. for 3 hours to form a terminal blocking site. The acid value was measured to confirm that 98% or more of the acid anhydride had reacted, and the reaction was terminated. Next, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% by mass, and a solution of dispersant (B1-R-1) with an acid value of 110 mg KOH / g and a weight average molecular weight of 9000 was obtained.

[0228] (Production example of dispersant (B1-R-2: comb-shaped)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 20.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid were charged and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added to 6.0 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours. It was confirmed that more than 95% of the monomers had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride, 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C for 5 hours. By measuring the amount of residual acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C for 3 hours to form a terminal blocking site. The acid value was measured, and it was confirmed that 98% or more of the acid anhydride had reacted, and the reaction was terminated. Next, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 30% by mass, and a solution of dispersant (B1-R-2) with an acid value of 105 mg KOH / g and a weight average molecular weight of 9400 was obtained.

[0229] (Production example of dispersant (B1-R-3: comb-shaped)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of pyromellitic dianhydride, and 70.8 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 ° C and reacted for 5 hours. By measuring the amount of remaining acid anhydride, it was confirmed that 80% of the acid anhydride had reacted. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120 ° C for 3 hours to form a terminal blocking site. After measuring the acid value and confirming that 98% or more of the acid anhydride had reacted, the temperature of the reaction system was cooled to 70 ° C, 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged, and 38.0 parts of propylene glycol monomethyl ether acetate in which 0.1 parts of 2,2'-azobisisobutyronitrile had been dissolved was added and reacted for 10 hours. The reaction was terminated when it was confirmed by measuring the non-volatile content that 95% or more of the monomers had reacted. After the reaction was terminated, propylene glycol monomethyl ether acetate was added so that the non-volatile content became 30% by mass, and a solution of dispersant (B1-R-3) with an acid value of 93 mgKOH / g and a weight average molecular weight of 10,800 was obtained.

[0230] (Production of resin-type dispersant (B1-1: comb-shaped)) A reaction vessel equipped with a gas inlet tube, a thermostat, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate (PGMAc), and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% or more of the monomer had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride groups had been half-esterified by measuring the acid value, and the solution was diluted with PGMAc so that the non-volatile content reached 30% by measuring the non-volatile content, thereby obtaining a resin-type dispersant (B1-1) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0231] (Production of resin-type dispersant (B1-2: comb-shaped, thermal crosslinking)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 160 parts of n-butyl acrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko Co., Ltd.: containing a blocked isocyanate group which is a thermal crosslinking group), 50 parts of propylene glycol monomethyl ether acetate, and 50 parts of cyclohexanone were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, 12 parts of 3-mercapto-1,2-propanediol were added, and the reaction was carried out for 12 hours. It was confirmed that 95% or more of the monomers had reacted by measuring the non-volatile content. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. The nonvolatile content was adjusted to 30% with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-2) having an acid value of 42 mgKOH / g and a weight average molecular weight of 9000, the resin-type dispersant containing a blocked isocyanate group that is a thermal crosslinkable group.

[0232] (Production of resin-type dispersant (B1-3: comb-shaped, photocrosslinkable)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% or more of the monomer had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a resin-type dispersant (B1-3) solution containing a (meth)acryloyl group, which is a photocrosslinking group, with a non-volatile content of 30%. The acid value of the obtained dispersant was 68 mgKOH / g, the double bond equivalent was 1593, and the weight average molecular weight was 13,000.

[0233] (Production of resin-type dispersant (B1-4: linear type)) In a reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and 4.4 parts of 3-mercapto-1,2-propanediol was added, followed by adding 0.2 parts of 2,2'-azobisisobutyronitrile in 20 batches every 30 minutes, and reacting at 80°C for 12 hours. It was confirmed that more than 95% of the monomers had reacted by measuring the non-volatile content. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 2 hours at 120°C and 5 hours at 80°C. It was confirmed by titration that more than 90% of the acid anhydride was half-esterified, and a resin-type dispersant (B1-4) with an acid value of 44 mgKOH / g per non-volatile content was obtained. Furthermore, a dispersant (B1-4) solution with a non-volatile content of 30% was obtained by adjusting the non-volatile content with PGMAc.

[0234] (Manufacture of resin-type dispersant (B1-5: linear type, heat curing)) In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine were charged. After replacing with nitrogen gas, the inside of the reaction vessel was heated to 120°C and reacted for 4 hours, and then reacted at 80°C for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA (methacrylate (3-ethyloxetan-3-yl) methyl, manufactured by Ube Industries), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes while maintaining the inside of the reaction vessel at 80°C. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% or more of the monomer had reacted. The solution was diluted with PGMAc so that the non-volatile content was 30% by non-volatile content measurement, and a resin-type dispersant (B1-5) solution containing a tertiary butyl group (tert-butyl group) and an oxetane group, which are thermosetting groups, was obtained, the acid value per non-volatile content being 51 mgKOH / g and the weight average molecular weight (Mw) being 24,000.

[0235] (Production of Resin-Type Dispersant (B2)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and after replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C for 4 hours. After confirming that 98% or more of the monomer had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride were added and reacted at 120 ° C for 2 hours. The reaction was terminated when it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. A dispersant (B2) solution with a non-volatile content of 30% was obtained by adjusting the non-volatile content with PGMAc. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mg KOH / g.

[0236] (Manufacture of other acidic resin-type dispersants (B3)) A thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirring device were attached to a separable 4-neck flask, and 1500 parts of cyclohexanone were charged. The temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. A mixed solution of 120 parts of methyl methacrylate, 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M-110" manufactured by Toagosei Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate, and 30 parts of 2,2'-azobisisobutyronitrile was dripped from the drip tube over 2 hours. After the dripping was completed, the reaction was continued for another 3 hours to obtain an acidic resin type dispersant (B3) solution with a non-volatile content of 30% and a weight average molecular weight of 24,000.

[0237] (Production of Basic Resin-Type Dispersant (Bb-1)) In a reactor equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the nonvolatile content. The reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin type dispersant (Bb-1) with an amine value per nonvolatile content of 169.8 mg KOH / g was obtained. After cooling to room temperature, about 2 g of the resin type dispersant 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 basic resin type dispersant (Bb-1) so that the nonvolatile content was 30 mass% to prepare a basic resin type dispersant (Bb-1) solution of ABA block polymer.

[0238] (Production of Basic Resin-Type Dispersant (Bb-2)) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110°C while replacing with nitrogen. A dropping vessel was charged with 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and the mixture was stirred until it became uniform, and then dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (Bb-2) with an amine value of 201 mgKOH / g per nonvolatile content and a number average molecular weight of 3,800 (Mn) was obtained. The solution was diluted in the same manner as the basic resin type dispersant (Bb-2) solution so that the nonvolatile content was 30% by mass, and a basic resin type dispersant (Bb-2) solution of a random polymer was prepared.

[0239] <Production example of binder resin (C)> (Preparation of binder resin (C-1) liquid) A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 196 parts of cyclohexanone, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. From the dropping tube, a mixture of 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.), and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20% to prepare a binder resin (C-1) liquid. The weight average molecular weight (Mw) was 26,000.

[0240] (Preparation of binder resin (C-2) liquid) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370 parts of cyclohexanone, heated to 80°C, and the flask was replaced with nitrogen. From the dropping tube, a mixture of 18 parts of paracumylphenol 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 was dropped over 2 hours. After the dropping, 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 continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (corresponding to 100 mol% of glycidyl groups) was added to 0.5 parts of trisdimethylaminophenol and 0.1 parts of hydroquinone. The reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (corresponding to 100 mol% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare a binder resin (C-2) liquid. The weight average molecular weight (Mw) was 19,000.

[0241] (Preparation of binder resin (C-3) liquid) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the whole amount of the obtained copolymer solution was stirred while injecting dry air for 1 hour, and then cooled to room temperature. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution synthesized earlier so that the non-volatile content was 20% to prepare a binder resin (C-2). The weight average molecular weight (Mw) was 18,000.

[0242] (Preparation of binder resin (C-4) liquid) A separable flask with a cooling tube was prepared as a reaction vessel, and a monomer dropping vessel was prepared by thoroughly stirring and mixing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats), and 40 parts of PGMAc. A chain transfer agent dropping vessel was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of PGMAc. 395 parts of PGMAc were charged into the reaction vessel, and after nitrogen replacement, the temperature of the reaction vessel was heated in an oil bath while stirring to raise the temperature to 90°C. After the temperature of the reaction vessel was stabilized at 90°C, dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. Dropping was carried out over 135 minutes, respectively, while maintaining the temperature at 90°C. 60 minutes after the end of the dripping, the temperature was raised to 110°C. After maintaining 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and reacted at 110°C for 12 hours. After that, 150 parts of PGMAc were added and cooled to room temperature, about 2g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20% by mass to obtain a binder resin (C-4) liquid. The weight average molecular weight of the resin was 18000, and the acid value per non-volatile content was 2mgKOH / g.

[0243] <Method of producing colored composition> [Production Example 1] (Preparation of Coloring Composition (R-1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (R-1) with a non-volatile content of 24.3% by mass. Fine pigment (A1-1): 20.5 parts Resin-type dispersant ((B1-R-1): 30% non-volatile liquid): 2.0 parts Binder resin (C-1: 20% non-volatile liquid): 16.0 parts Solvent (P): 61.5 parts

[0244] [Manufacturing Examples 2-30] (Preparation of Colored Compositions (R-2 to R-30)) Colored compositions (R-2) to (R-30) were prepared in the same manner as in Production Example 1, except that the material types and masses were changed as shown in Table 2. The dispersed particle diameters of each are shown in Table 2.

[0245] [Table 2]

[0246] <Method for producing photosensitive coloring composition> [Example 1] (Photosensitive coloring composition (X-1)) The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1). Coloring composition 1 (R-1: non-volatile content 24.3%): 50.0 parts Coloring composition 2 (R-23: non-volatile content 24.3%): 20.0 parts Binder resin (C-2: non-volatile content 20%): 10.0 parts Polymerizable compound (D1-1): 3.0 parts Photopolymerization initiator (E1-1): 1.8 parts Thermosetting compound (CE-1): 1.0 part Thermosetting compound (CE-2): 1.0 part Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 part Ultraviolet absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M: non-volatile content 3%): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 parts Solvent (P): 11.0 parts

[0247] [Examples 2 to 55, Comparative Example 1] (Preparation of Photosensitive Coloring Compositions (X-2 to 56)) Photosensitive coloring compositions (X-2 to 56) were prepared in the same manner as in Example 1, except that the types of the photosensitive coloring composition and the binder resin solution in Example 1 were changed as shown in Tables 3-1 to 3-6.

[0248] The raw materials are as follows: <Polymerizable compound (D)> (D1-1) Polymerizable compound having a secondary hydroxyl group [Propylene glycol diglycidyl ether diacrylate] (In general formula (3), X is general formula (4), n=1, R 1 = hydrogen atom, R 2 = represented by hydrogen atoms) (D1-2) Polymerizable compound having a secondary hydroxyl group [1,4-butanediol diglycidyl ether diacrylate] (In general formula (3), X is general formula (5), n=4, R 1 = hydrogen atom, R 2 = represented by hydrogen atoms) (D1-3) Polymerizable compound having a secondary hydroxyl group [Glycerol diglycidyl ether diacrylate] (In the general formula (3), X is the general formula (6), n=1, R 1 = hydrogen atom, R 2 = represented by hydrogen atoms) (D-2) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei)] (D-3) EO modified (12) Dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku)] (D-4) Mixture of dipentaerythritol penta- and hexaacrylate [Aronix M402 (manufactured by Toagosei)]

[0249] <Photopolymerization initiator (E)> The compounds (E1-1), (E1-2), (E2-1), and (E3-1) to (E3-7) used were the compounds already exemplified. (E4-1) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (manufactured by BASF Japan)] (E5-M) Below, (E5-1) to (E5-7) were mixed in equal amounts to prepare a photopolymerization initiator (E5-M). (E5-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (BASF Japan)] (E5-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (BASF Japan)] (E5-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (IGM Resins)] (E5-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (Kurokane Chemicals)] (E5-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine)] (E5-6) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (BASF Japan)] (E5-7) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (BASF Japan)]

[0250] <Thermosetting compound (CE)> Epoxy compound (CE-1) (CE-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel)], (CE-1-2) Glycidyl etherified epoxy compounds of sorbitol [Denacol EX611 (Nagase ChemteX)] (CE-1-3) Triglycidyl isocyanurate Equal amounts of (CE-1-1) to (CE-1-3) were mixed to prepare an epoxy compound (CE-1). Oxetane compounds (CE-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei)]

[0251] <Sensitizer (H)> (H-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku)] (H-2) 4,4'-Bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] The above (H-1) and (H-2) were mixed in equal amounts to prepare sensitizer (H).

[0252] <Thiol-based chain transfer agents (I)> (I-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)] (I-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (Showa Denko)] (I-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-5) Tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (I-1) to (I-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (I).

[0253] <Polymerization inhibitor (J)> (J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) tert-Butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

[0254] <Ultraviolet absorber (K)> (K-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN400 (BASF Japan)] (K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] The above (K-1) and (K-2) were mixed in equal amounts to prepare an ultraviolet absorber (K).

[0255] <Antioxidants (L)> (L-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) Dioctadecyl 3,3'-thiodipropanoate (L-3) Tris[2,4-di-(tert)-butylphenyl]phosphine (L-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-Octylphenyl Salicylate The above (L-1) to (L-5) were mixed in equal amounts to prepare an antioxidant (L).

[0256] <Leveling agent (M)> A mixed solution of 1 part of BYK-330 manufactured by BYK, 1 part of Megafac F-551 manufactured by DIC, and 1 part of Emulgen 103 manufactured by Kao, dissolved in 97 parts of PGMAc.

[0257] <Storage stabilizer (N)> (N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (Honshu Chemical Industry Co., Ltd. "BHT") (N-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) The above (N-1) and (N-2) were mixed in equal amounts to prepare a storage stabilizer (N).

[0258] <Adhesion improver (O)> (O-1) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (O-1) to (O-4) were mixed in equal amounts to prepare a silane coupling agent (O).

[0259] <Solvent (P)> (P-1) PGMAc 30 copies (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above-mentioned parts by mass to prepare a solvent (P).

[0260] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions (X-1 to X-56) were subjected to the following tests. The test results are shown in Tables 3-1 to 3-4. The evaluation criteria are as follows: 4: Particularly good level. 3: Good level. 2: Practical level. 1: Impractical level.

[0261] <Creating evaluation pixels> The obtained photosensitive coloring composition was spin-coated on a glass substrate using a spin coater so that the dry film thickness was 0.5 μm, and pre-baked at 120° C. for 120 seconds. Next, after cooling the substrate to room temperature, a KrF scanner exposure machine was used to expose the substrate to 200 mJ / cm 2 through a mask having a Bayer pattern with a pixel (pattern) size of 2 μm square. 2 The sample was exposed to a pulse of KrF radiation at an exposure of 250,000,000 W / m 2 (Average illuminance: 30,000W / m 2 ), pulse width: 30 nanoseconds, frequency: 4 kHz). The substrate was then spray-developed using a 0.2% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) at 23°C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 200°C for 10 minutes to create evaluation pixels of 2 μm square on the substrate.

[0262] <Coloring power> The transmission spectrum of the obtained evaluation pixel was measured using a microspectrophotometer (Olympus Optical Co., Ltd., "OPS-SP100"). The measurement results were evaluated according to the following criteria. Note that by reducing the transmittance in the vicinity of 530 nm, the color separation between each pixel of the color filter is improved, and the image quality of image sensors and display devices is improved. 3: Transmittance of 530 nm wavelength is less than 0-6% 2: Transmittance of 530 nm wavelength is 6% or more but less than 10% 1: Transmittance of 10% or more at a wavelength of 530 nm

[0263] <Developability (residue in unexposed areas)> The obtained evaluation pixels were observed using an electron microscope (magnification: 20,000 times) to confirm the number of residues present in the areas that were not irradiated with light during the exposure process (unexposed areas). The evaluation criteria are as follows: 3: 0 to 3 residues in the unexposed area of ​​2 μm square 2: 4 to 10 residues in a 2 μm square area of ​​unexposed area 1: 11 or more residue particles in a 2 μm square area of ​​unexposed area

[0264] <Rectangularity evaluation> The cross-sectional shape of the obtained evaluation pixel was confirmed by an electron microscope. The evaluation criteria were as follows: 3: The angle between the substrate and the pixel edge is 80° or more and less than 100° 2. Pixels with an angle between the substrate and the pixel edge of 70° or more and less than 80° are slightly tapered. 1; Pixels with an angle of less than 70° between the substrate and the pixel edge are tapered or have an overhang of 100° or more.

[0265] <Adhesion evaluation> Except for changing the mask size used in the fabrication of the evaluation pixels to 0.6 μm square, 1 μm square, or 1.5 μm square, the same development and washing processes were carried out as above to fabricate the evaluation pixels. The obtained evaluation pixels were observed to see if they remained on the substrate without peeling off during the development and washing processes. 4: All 0.6 μm square, 1 μm square, and 1.5 μm square pixels remain. 3: There is some peeling of the 0.6 μm square, but all of the 1 μm square and 1.5 μm square pixels remain. 2: There is some peeling on the 0.6 μm square and 1 μm square pixels, but all of the 1.5 μm square pixels remain. 1: There was some peeling in the 1.5 μm square pixel.

[0266] <Viscosity characteristics> The viscosity 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 criteria are as follows. 3: Viscosity: 2.0 or more and less than 10.0 1: Viscosity 10.0 or more

[0267] <Storage stability> The storage stability of the obtained photosensitive coloring composition was evaluated by the following method. The initial viscosity of the photosensitive coloring composition on the day after preparation and the viscosity over time after aging at 40° C. for one week were measured using an E-type viscometer (TOKI SANGYO CO., LTD.'s "ELD type viscometer") at 25° C. and a rotation speed of 50 rpm. From the initial viscosity and the viscosity over time values, the viscosity change rate over time was calculated using the following formula, and the storage stability was evaluated in two stages. [Change rate of viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 3: The rate of change is less than 10% 2: The rate of change is between 10% and 20% 1: Change rate is 20% or more

[0268] [Table 3-1]

[0269] [Table 3-2]

[0270] [Table 3-3]

[0271] [Table 3-4]

[0272] [Table 3-5]

[0273] [Table 3-6] [Explanation of symbols]

[0274] 10 LCD 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

1. A photosensitive coloring composition for use in a color filter that is patterned by pulsed exposure to ultraviolet light having a wavelength of 250 nm or less, comprising: The composition comprises a colorant (A), a resin-type dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), A photosensitive coloring composition, characterized in that the colorant (A) contains a pigment (A1) represented by the following general formula (1) and a yellow colorant (A3). General formula (1) 【Chemistry 1】 (In general formula (1), R １ represents any one of a hydroxy group, an alkyl group, an alkoxy group, an alkylthio group, an aryloxy group, an alkylamino group, and an amino group.

2. The photosensitive coloring composition according to claim 1, characterized in that the resin type dispersant (B) comprises an aromatic carboxylic acid ester moiety and a vinyl polymer moiety, and the aromatic carboxylic acid ester moiety comprises a resin type dispersant (B1-R) having a sealing moiety derived from an end-capping material.

3. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (E) comprises one or more oxime ester compounds selected from the group consisting of the following (E1), (E2) and (E3): (E1) Compound having two oxime ester groups and a carbazole skeleton (E2) Compound having two oxime ester groups and a phenothiazine skeleton (E3) A compound represented by the following general formula (2): General formula (2) 【Chemistry 2】 (In general formula (2), R ２ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. ３ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. ４ R represents a branched alkyl group having 6 or more carbon atoms or a cyclic organic group. ５ represents a monovalent substituent (excluding an oxime ester group); and n represents an integer of 0 to 3.

4. The photosensitive coloring composition according to claim 1, wherein the polymerizable compound (D) comprises a compound (D1) represented by the following general formula (3): General formula (3) 【Chemistry 3】 (In the general formula (3), X is a partial structure represented by the following general formula (4), general formula (5), or general formula (6). R １ , R ２ represents a hydrogen atom or a methyl group. 【Chemistry 4】 (In the general formula (4), n represents an integer of 1 to 4, and R ３ represents a hydrogen atom or a methyl group. In formula (5), n represents an integer of 1 to 4. In formula (6), n represents an integer of 1 to 4.

5. A color filter having filter segments formed from the photosensitive coloring composition according to any one of claims 1 to 4.

6. A solid-state imaging device comprising the color filter according to claim 5.

7. A liquid crystal display device comprising the color filter according to claim 5.

Images