Red photosensitive composition, film, color filter, solid-state imaging element, and image display device

Abstract

The purpose of the present invention is to provide a red photosensitive composition having excellent storage stability and capable of forming a film having excellent resistance after low-temperature heating. The above-mentioned problem can be solved by a red photosensitive composition comprising a colorant (A), a resin (B) having an acidic group, a polymerizable compound (C), and a polymerization initiator (D), the colorant (A) comprising a red colorant (A1) and a yellow colorant (A2), the red color material (A1) contains one or more substances selected from the group consisting of C. I. Pigment Red 179 and C. I. Pigment Red 264, the yellow color material (A2) contains an isoindoline pigment, and the polymerization initiator (D) contains a polymerization initiator (D1) in which the light absorption coefficient of light having a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0 * 10 < 3 > L / mol.cm or more.

Description

Technical Field

[0001] The present invention relates to a red photosensitive composition for forming a color filter or the like. Background Art

[0002] Color filters are usually prepared by forming patterns by photolithography. The photosensitive composition used to manufacture color filters is usually stored for several weeks to several months after manufacture and then used. Therefore, there are problems such as foreign matter generated in the photosensitive composition during storage, and the photosensitive composition changes over time, resulting in deviations in film thickness, pattern shape, etc. during pattern formation.

[0003] In addition, due to the miniaturization and high pixelization of image display devices and solid-state imaging elements, the area of ​​each pixel tends to become smaller, and the color filter is required to be thinner. Therefore, the concentration of the color material contained in the pixel of the color filter becomes higher, and the components other than the color material are relatively reduced. As a result, there is a problem of deterioration in developability and pattern formation.

[0004] Furthermore, in recent years, from the viewpoint of environmental issues, it has been required to lower the temperature in the above-mentioned post-baking process. As a result, there has been a problem that curing in the post-baking process is insufficient and the resistance is deteriorated.

[0005] Therefore, Patent Document 1 discloses a color material composition for color filters, which is aimed at excellent color material dispersion stability, reduced phase difference value, improved contrast, and color reproducibility, and includes red color materials and yellow color materials, and the yellow color materials include specific azo compounds and anions of azo compounds with tautomeric structures, at least two specific metal ions and specific compounds, and the dispersant includes a polymer with a specific structural unit. Patent Document 2 discloses an organic pigment composition for color filters, which is aimed at improving dispersion stability, includes perylene organic pigments and organic pigment derivatives containing sulfonic groups, and the primary particle size of the pigment is 20nm to 100nm. Patent Document 3 discloses a red pigment dispersion resist composition for color filters, which is aimed at excellent dispersion stability, high tinting power and high brightness, and includes a specific red pigment, a pigment dispersing aid with a specific structure, a polymer pigment dispersant containing a basic group, an alkaline soluble resin, and an organic solvent.

[0006] In addition, Patent Document 4 discloses a colored photosensitive composition, which contains a colorant, a polymerizable compound and a photopolymerization initiator for the purpose of improving curability under low temperature environment, wherein the absorbance of a solution of the photopolymerization initiator dissolved in acetonitrile at 0.001 mass % is 0.45 or more at a wavelength of 340 nm. Patent Document 5 discloses a colored resin composition, which contains a pigment, a resin, a polymerizable compound and a polymerization initiator for the purpose of low temperature curability and improving the color reproducibility of red, wherein the pigment includes CI Pigment Violet 19, a red pigment and a yellow pigment. Patent Document 6 discloses a curable resin composition, which contains the following resin for the purpose of forming a cured film with excellent solvent resistance and adhesion even if the temperature of the post-baking process is 200°C or less: a structural unit having an α,β-unsaturated carbonyl group, a structural unit having an active methylene group or an active methine group, and a structural unit having an acid group.

[0007] Patent Document 1: International Publication No. 2018 / 124087

[0008] Patent Document 2: International Publication No. 2015 / 015962

[0009] Patent Document 3: Japanese Patent Application Publication No. 2015-79161

[0010] Patent Document 4: International Publication No. 2017 / 038708

[0011] Patent Document 5: International Publication No. 2021 / 131834

[0012] Patent Document 6: Japanese Patent Application Publication No. 2022-10246 Summary of the invention

[0013] However, the compositions described in Patent Documents 1 to 6 cannot all satisfy certain levels of storage stability, developability, pattern forming properties, and film resistance after low-temperature heating.

[0014] An object of the present invention is to provide a red photosensitive composition which is excellent in storage stability, developability, and pattern forming property and can form a film having excellent resistance after low-temperature heating.

[0015] The red photosensitive composition of the present invention comprises a color material (A), a resin having an acidic group (B), a polymerizable compound (C), and a polymerization initiator (D).

[0016] The color material (A) includes a red color material (A1) and a yellow color material (A2).

[0017] The red color material (A1) includes at least one selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264.

[0018] The yellow color material (A2) includes an isoindoline pigment.

[0019] The polymerization initiator (D) contains propylene glycol monomethyl ether acetate, and the absorption coefficient of light with a wavelength of 365 nm is 5.0×10 3 The polymerization initiator (D1) has a polymerization amount of at least L / mol·cm.

[0020] According to the present invention, a red photosensitive composition having excellent storage stability, developability, and pattern formation properties and capable of forming a film having excellent resistance after low temperature heating can be provided. In addition, the present invention can provide a film, a color filter, a solid-state imaging element, and an image display device. DETAILED DESCRIPTION

[0021] Hereinafter, the mode for implementing the red photosensitive composition of the present invention will be described in detail. In addition, the present invention is not limited to the following embodiments, and can be implemented by modification within the scope that can solve the technical problem.

[0022] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic acid", "(meth)acrylic acid", "(meth)acrylate" or "(meth)acrylamide" means "acryloyl and / or methacryloyl", "acrylic acid and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate" or "acrylamide and / or methacrylamide", respectively. In addition, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists).

[0023] In the present specification, the polymerizable unsaturated group is an ethylenically unsaturated double bond.

[0024] In this specification, a monomer is a compound that forms a resin by polymerization. A monomer is an unreacted state, and a monomer unit is a state in which a resin is formed after polymerization of the monomer.

[0025] In this specification, the low molecular weight compound whose molecular weight can be specified is a value calculated by calculation (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the compound having a molecular weight distribution is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.

[0026] In the present specification, a numerical range expressed using "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0027] <Red photosensitive composition>

[0028] The red photosensitive composition according to one embodiment of the present invention includes a color material (A), a resin having an acidic group (B), a polymerizable compound (C), and a polymerization initiator (D).

[0029] The color material (A) includes a red color material (A1) and a yellow color material (A2).

[0030] The red color material (A1) includes at least one selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264.

[0031] The yellow color material (A2) includes an isoindoline pigment.

[0032] The polymerization initiator (D) contains propylene glycol monomethyl ether acetate, and the absorption coefficient of light with a wavelength of 365 nm is 5.0×10 3 The polymerization initiator (D1) has a polymerization amount of at least L / mol·cm.

[0033] The mechanism by which the red photosensitive composition having the above-mentioned structure can solve the technical problem of the present invention is not clear, but is presumed as follows.

[0034] CI Pigment Red 179 and CI Pigment Red 264 as red colorants (A1) have poor dispersion stability. Therefore, when a red photosensitive composition containing these red colorants (A1) is stored for a long time, foreign matter is easily generated due to the association and aggregation of the red colorants (A1). However, it is speculated that by using an isoindoline pigment and a resin (B) having an acidic group, the association and aggregation of the red colorant (A1) during storage is suppressed, thereby improving the storage stability. In addition, compared with the case of using a resin having a basic group, the solubility in an alkaline aqueous solution is improved. Therefore, it is speculated that the residue during development is suppressed and the pattern forming property is improved. Furthermore, it is speculated that by using propylene glycol monomethyl ether acetate, the absorption coefficient of light with a wavelength of 365 nm is 5.0×10 3 The polymerization initiator (D1) having a polymerization initiator concentration of L / mol·cm or more can easily cause a photoreaction as the polymerization initiator (D), and can maintain the same film resistance as that of a film heated at a high temperature even when heated at a low temperature.

[0035] Hereinafter, the components contained or which may be contained in the red photosensitive composition of the present invention will be described in detail.

[0036] [Color material (A)]

[0037] The colorant (A) is not particularly limited, and examples thereof include chromatic colorants such as red, yellow, blue, violet, green, and orange, achromatic colorants such as white and black, near infrared absorbing colorants, and fluorescent colorants.

[0038] In addition, in this specification, the white color material includes not only pure white but also a light gray (eg, off-white, light gray) color material that is close to white.

[0039] The color material (A) may be any of a pigment and a dye, or a pigment and a dye may be used in combination.

[0040] The pigment may be any of an inorganic pigment and an organic pigment, or a combination of an inorganic pigment and an organic pigment. In addition, the pigment may also be an organic-inorganic composite.

[0041] The pigment is preferably micronized for use. The micronization method is not particularly limited, for example, any of wet grinding, dry grinding, and dissolution separation can be used. Among them, salt milling treatment based on a kneading method is preferred as a type of wet grinding. The average primary particle size of the micronized pigment determined by TEM (transmission electron microscopy) is preferably 5nm to 90nm. In addition, from the viewpoint of dispersibility, the average primary particle size is more preferably 10nm to 70nm.

[0042] The content of the color material (A) is preferably 0.5% by mass to 60% by mass, and more preferably 1% by mass to 50% by mass, in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0043] (Red color material (A1))

[0044] The red photosensitive composition of the present invention contains a red color material (A1), and the red color material (A1) contains at least one selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264.

[0045] The red color material (A1) preferably contains CI Pigment Red 264 from the viewpoint of light resistance.

[0046] The total content of CI Pigment Red 179 and CI Pigment Red 264 is preferably 60 to 100% by mass, more preferably 80 to 100% by mass, in 100% by mass of the red color material (A1).

[0047] The red color material (A1) may include red color materials other than CI Pigment Red 179 and CI Pigment Red 264.

[0048] Red color materials other than CI Pigment Red 179 and CI Pigment Red 264 may use known compounds. 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、181、 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260 0, 262, 263, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, 297, a red pigment described in Japanese Patent Application Publication No. 2014-134712, a pigment described in Japanese Patent No. 6368844, and the like.

[0049] In addition, red dyes such as CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 150, 151, 158, 176, 183, 198, 211, 251, 216, 217, 249, 252, 257, 260, 266, and 274, and lakes, salt compounds, polymers, and the like of these red dyes can be mentioned.

[0050] The content of the red color material (A1) is preferably 60 to 99% by mass, more preferably 70 to 95% by mass, in 100% by mass of the color material (A).

[0051] (Yellow color material (A2))

[0052] The red photosensitive composition of the present invention contains a yellow color material (A2), and contains an isoindoline pigment as the yellow color material (A2).

[0053] Known isoindoline pigments may be used, and examples thereof include CI Pigment Yellow 109, 110, 137, 139, 173, 177, 179, 185, and pigments described in JP-A-2011-025194 and JP-A-2022-025209.

[0054] Among them, CI Pigment Yellow 139 and 185 are preferred, and CI Pigment Yellow 139 is more preferred, from the viewpoint of storage stability.

[0055] The content of the isoindoline pigment is preferably 60% by mass to 100% by mass, and more preferably 80% by mass to 100% by mass, in 100% by mass of the yellow color material (A2).

[0056] The yellow color material (A2) may contain a yellow color material other than the isoindoline pigment.

[0057] Yellow colorants other than isoindoline pigments may use known compounds. 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, 113, 114, 115, 116, 117, 118, 119, 120, 123, 124, 125 26, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 174, 175, 176, 180, 181, 182, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, 234, 235, 236, yellow pigments described in Japanese Patent Application Laid-Open No. 2012-226110.

[0058] In addition, examples of yellow pigments include one or more anions selected from the group consisting of mono-, di-, tri- and tetra-anions of azo compounds represented by the following general formula (1) and azo compounds having tautomeric structures thereof, at least two metal ions selected from the group consisting of Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu and Mn, and a metal azo pigment containing a compound represented by the following general formula (2).

[0059]

Chemistry 1

[0060] General formula (1)

[0061]

[0062] In the general formula (1), two R1s each independently represent -OH, -NH2, -NH-CN, acylamino, alkylamino or arylamino, and two R2s each independently represent -OH or -NH2.

[0063]

Chemistry 2

[0064] General formula (2)

[0065]

[0066] In the general formula (2), three R3 each independently represents a hydrogen atom or an alkyl group.

[0067] Examples of the metal azo pigment include those described in JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, and JP-A-2022-61494.

[0068] In addition, CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, CI Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 79, 82, 94, 98, 99, 162, Japanese Patent Application Publication No. 2019-073695, Japanese Patent Application Publication No. 2019-073696, Japanese Patent Application Publication No. 2019-073697, and Japanese Patent Application Publication No. 2019-073698, and yellow dyes having a methine structure, as well as lakes, salt compounds, polymers, and the like of these yellow dyes can be mentioned.

[0069] The content of the yellow color material (A2) is preferably 1% by mass to 40% by mass, and more preferably 5% by mass to 30% by mass, based on 100% by mass of the color material (A).

[0070] The red photosensitive composition of the present invention may contain a color material other than the red color material (A1) and the yellow color material (A2) as the color material (A).

[0071] As the color material other than the red color material (A1) and the yellow color material (A2), known compounds can be used, for example, chromatic color materials such as blue color materials, purple color materials, green color materials, and orange color materials, white color materials, and black color materials.

[0072] Among them, from the viewpoint of spectral characteristics, the color material other than the red color material (A1) and the yellow color material (A2) preferably includes one or more of the group consisting of a blue color material (A3) and a violet color material (A4).

[0073] (Blue color material (A3))

[0074] A known compound can be used as the blue color material (A3), for example, CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, 88 and the like blue pigments can be mentioned.

[0075] In addition, blue dyes such as CI Acid Blue 1, 7, 9, 15, 18, 23, 80, 90, CI Solvent Blue 5, 35, 36, 37, 44, 45, 59, 67, and lakes, salt compounds, polymers, and the like of these blue dyes can be cited.

[0076] Among them, the blue color material (A3) is preferably at least one selected from the group consisting of CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Blue 15:6, and CI Pigment Blue 16 from the viewpoint of light resistance.

[0077] The content of the blue color material (A3) is preferably 0.1% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass, based on 100% by mass of the color material (A).

[0078] (Purple color material (A4))

[0079] As the violet color material (A4), a known compound can be used, and examples thereof include violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0080] In addition, compounds having a triarylmethane skeleton such as CI Basic Violet 1, 3, and 14, compounds having a cyanine skeleton such as CI Basic Violet 7 and 16, compounds having an anthraquinone skeleton such as CI Solvent Violet 8, 13, 14, 21, 27, 28, and 36, compounds having a xanthene skeleton such as CI Acid Violet 9, 30, and 102, CI Basic Violet 10, 11, and 25, CI Acid Red 51, 52, 87, 92, 94, 289, 388, and 463, and lakes, salt-forming compounds, and polymers of these compounds can be cited.

[0081] Among them, from the viewpoint of brightness, the violet color material (A4) is preferably a compound having a xanthene skeleton.

[0082] The compound having a xanthene skeleton is not particularly limited as long as it has a xanthene skeleton, and a known compound can be used.

[0083] From the viewpoint of storage stability, the compound having a xanthene skeleton is more preferably a salt-forming compound of one or more dyes selected from CI Acid Red 52, 289, and 463, or a resin that forms a salt of these dyes.

[0084] The content of the violet color material (A4) is preferably 0.1% by mass to 15% by mass, and more preferably 0.5% by mass to 10% by mass, in 100% by mass of the color material (A).

[0085] [Resin having an acidic group (B)]

[0086] The resin (B) with an acidic group is used for the purpose of stabilizing the dispersed color material (A) and imparting resistance to the film. In addition, the resin (B) with an acidic group that is mainly used for dispersing the color material (A) is called a dispersion resin, and the resin (B) with an acidic group that is mainly used for imparting resistance to the film is called a binder resin. The resin (B) with an acidic group can have the functions of both a dispersion resin and a binder resin in one resin. However, this use of the resin (B) with an acidic group is an example, and it can also be used for purposes other than these. In addition, in this specification, the resin (B) with an acidic group refers to a resin in which the amount of acidic groups is greater than the amount of basic groups.

[0087] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among them, a carboxyl group and a phosphoric acid group are preferred from the viewpoint of storage stability.

[0088] The acid value of the resin (B) having an acidic group is preferably 30 to 250 mgKOH / g, more preferably 40 to 200 mgKOH / g.

[0089] The weight average molecular weight of the resin (B) having an acidic group is preferably 2,000 to 50,000, more preferably 4,000 to 40,000.

[0090] The resin (B) having an acidic group may be used alone or in combination of two or more.

[0091] The content of the resin (B) having an acidic group is preferably 1 to 60% by mass, more preferably 5 to 60% by mass, in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0092] (Resin having an aromatic carboxyl group (B1))

[0093] From the viewpoint of storage stability, the resin (B) having an acidic group preferably includes a resin (B1) having an aromatic carboxyl group as a dispersing resin. CI Pigment Red 179 and CI Pigment Red 264 contain a structure similar to an aromatic ring, and since they interact strongly with the aromatic carboxyl group, it is presumed that the resin (B1) having an aromatic carboxyl group will not be freed from the color material (A) during storage, and the dispersion stability of the color material (A) is maintained.

[0094] In addition, in this specification, an aromatic carboxyl group means a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring.

[0095] The aromatic carboxyl group may be contained in the main chain of the resin or in the side chain. From the viewpoint of storage stability, it is preferably contained in the main chain.

[0096] From the viewpoint of storage stability, the number of carboxyl groups bonded to the aromatic ring of the aromatic carboxyl group is preferably 1 to 4.

[0097] From the viewpoint of storage stability, the resin (B1) having an aromatic carboxyl group preferably comprises a resin having a main chain based on an aromatic carboxylate portion having an ester bond and a side chain based on an ethylene polymer portion, wherein the aromatic carboxylate portion having an ester bond is a reaction product of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups.

[0098] The aromatic carboxylate part of the main chain is obtained by a ring-opening reaction between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and an aromatic carboxyl group is generated simultaneously with the formation of an ester bond. The aromatic carboxyl group functions as an adsorption site for the color material (A).

[0099] The ethylene polymer part of the side chain functions as a steric repulsion part to suppress the association and aggregation of the color material (A). The ethylene polymer part of the side chain can be obtained by, for example, the following two methods.

[0100] The first method is a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups. The compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0101] The second method is a method of copolymerizing a monomer in the presence of a reaction product of an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having two or more hydroxyl groups.

[0102] The difference between the above two methods is whether the ethylene polymer part for copolymerizing the monomer is introduced first or later. Depending on various conditions, the molecular weight etc. may be slightly different, but if the raw materials and reaction conditions are the same, the same compound can be synthesized in theory.

[0103] The main chain and the side chain are described in detail below.

[0104] 〔Main chain〕

[0105] In the aromatic carboxylic acid ester moiety, an anhydride group of an aromatic compound having two or more anhydride groups is obtained by a ring-opening reaction with a compound having two or more hydroxyl groups.

[0106] Examples of the aromatic compound having two or more acid anhydride groups include compounds represented by the following general formula (3) and general formula (4).

[0107]

Chemistry 3

[0108]

[0109] In the general formula (3), n represents 1 or 2.

[0110] In the general formula (4), Q represents a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following general formula (5) or a group represented by the following general formula (6).

[0111]

Chemistry 4

[0112]

[0113] Examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol trimellitic anhydride, propylene glycol trimellitic anhydride, butanediol trimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic 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'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid 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 Anhydride, 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 acid dianhydride or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride, etc. Among them, aromatic tetracarboxylic acid dianhydrides are preferred, and pyromellitic acid dianhydride is more preferred.

[0114] As described above, the compound having two or more hydroxyl groups is preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0115] Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethylenediol, 3-mercapto-1,2-propanediol (thioglycerol), 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.

[0116] From the viewpoint of storage stability, the aromatic carboxylate site is preferably a reaction site of 0.9 to 1.5 moles of an aromatic compound having two or more anhydride groups relative to 1 mole of a compound having two or more hydroxyl groups. It is more preferably a reaction site of 1.0 to 1.3 moles of an aromatic compound having two or more anhydride groups relative to 1 mole of a compound having two or more hydroxyl groups. Storage stability is improved by increasing the ratio of the adsorption site to the color material (A), i.e., the aromatic carboxyl group. Theoretically, when the aromatic compound having two or more anhydride groups exceeds 1 mole, the terminal is an anhydride group.

[0117] In addition, the anhydride group at the end of the aromatic carboxylic acid ester site can react with a monoalcohol. That is, the anhydride group is ring-opened with the monoalcohol to generate an alcohol ester and a carboxyl group. As a result, the solubility in the developer is improved and the developability is improved. In addition, a monoamine can be used instead of a monoalcohol.

[0118] The monoalcohols include, for example, methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, tert-pentanol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononanol, 1-nonanol, amyl alcohol, lauryl alcohol, n-butanol, isobutanol, cyclohexanol, benzyl alcohol, methylcyclohexanol and the like;

[0119] 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 monotert-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;

[0120] Monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate and diacetone alcohol.

[0121] Among them, from the viewpoint of developability, compounds having an ether group or a carbonyl group are preferred, and 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are more preferred. The monoalcohol may be used alone or in combination of two or more.

[0122] The amount of the monoalcohol used relative to the acid anhydride group is preferably 1 to 30 equivalents, more preferably 1.5 to 20 equivalents, relative to 1 equivalent of the acid anhydride group in the main chain.

[0123] 〔Sidechain〕

[0124] As described above, the ethylene polymer moiety can be synthesized by copolymerizing monomers in the presence of a compound having two or more hydroxyl groups or by copolymerizing monomers in the presence of a reaction product of an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having two or more hydroxyl groups.

[0125] Examples of the monomer include linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isopentyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, hexadecyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, methoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, or methoxypolyethylene glycol polypropylene glycol (meth)acrylate;

[0126] Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate;

[0127] Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate;

[0128] (Meth)acryloyloxy-modified polydimethylsiloxane (organic silicone macromonomer);

[0129] (Meth)acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate;

[0130] (Meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate;

[0131] (Meth)acrylic acid, acrylic acid dimer, ethyl 2-(meth)acryloxyphthalate, propyl 2-(meth)acryloxyphthalate, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate, etc. (meth)acrylate having a carboxyl group;

[0132] Ethylene such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate or allyl (meth)acrylate;

[0133] N-substituted (meth)acrylamide such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide or acryloylmorpholine;

[0134] (Meth)acrylates containing an amino group such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate;

[0135] (Meth) acrylonitrile and other nitriles;

[0136] 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;

[0137] Fatty acid vinyl esters such as vinyl acetate and vinyl propionate;

[0138] Monomers containing acidic groups such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0139] From the viewpoint of film resistance after low temperature heating, the ethylene polymer part preferably contains one or more of a thermally crosslinkable group and a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetane group, a tert-butyl group, and a blocked isocyanate group.

[0140] The heat-crosslinkable group can be introduced by using a monomer having a hydroxyl group, an epoxy group, an oxetane group, a tert-butyl group, a blocked isocyanate group, or the like.

[0141] The polymerizable unsaturated group can be introduced, for example, by reacting a hydroxyl group present in the vinyl polymer portion with an isocyanate group of a monomer having an isocyanate group.

[0142] The synthesis of the resin (B1) having an aromatic carboxyl group is preferably carried out, for example, by polymerizing the monomer radicals in the presence of a compound having two or more hydroxyl groups, i.e., a compound having two hydroxyl groups and a thiol group at one end (a), to generate an ethylene polymer having two hydroxyl groups at one end, and reacting it with an aromatic compound having two or more acid anhydride groups, i.e., tetracarboxylic dianhydride (b). Furthermore, when the terminal of the resin is an acid anhydride group, if it reacts with a monoalcohol, an encapsulation site from the monoalcohol can be introduced.

[0143]

Chemistry 5

[0144]

[0145] In (c), X is a reaction residue after the tetracarboxylic dianhydride (b) reacts with a hydroxyl group, Z is a reaction residue after the compound having two hydroxyl groups reacts with an acid anhydride group, and R is a residue of a monoalcohol.

[0146] The polymerization temperature of the ethylene polymer portion is preferably 40 to 150° C., more preferably 50 to 110° C. When the temperature is 40° C. or higher, polymerization proceeds easily, and when the temperature is 150° C. or lower, molecular weight control is easy.

[0147] In the polymerization of the ethylene polymer moiety, a polymerization initiator may be used in an amount of 0.001% to 5% by mass based on the total monomer mass of the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0148] Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane 1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile) or 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0149] Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiator may be used alone or in combination of two or more.

[0150] The ethylene polymer part is preferably synthesized by bulk polymerization or solution polymerization. For example, the polymerization solvent for solution polymerization may include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate or diethylene glycol monobutyl ether acetate. The polymerization solvent may be used alone or in combination of two or more.

[0151] In the synthesis of the aromatic carboxylic acid ester site, a reaction catalyst can be used. The reaction catalyst is preferably a tertiary amine compound. Examples of tertiary amine compounds include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0152] In the synthesis of the aromatic carboxylic acid ester site, solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile, and propylene glycol monomethyl ether acetate can be used.

[0153] The synthesis temperature of the aromatic carboxylic acid ester moiety is preferably 50°C to 180°C, more preferably 80°C to 140°C.

[0154] The acid value of the resin (B1) having an aromatic carboxyl group is preferably 20 to 250 mgKOH / g, more preferably 30 to 200 mgKOH / g.

[0155] The weight average molecular weight of the resin (B1) having an aromatic carboxyl group is preferably from 2,000 to 40,000, more preferably from 4,000 to 30,000.

[0156] The resin (B1) having an aromatic carboxyl group can be used alone or in combination of two or more.

[0157] From the viewpoint of storage stability, the resin (B1) having an aromatic carboxyl group is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, in 100% by mass of the resin (B) having an acidic group.

[0158] (Resin (B2) not having an aromatic carboxyl group)

[0159] From the viewpoint of film resistance after low-temperature heating, the resin (B) having an acidic group preferably contains a resin (B2) having no aromatic carboxyl group as a binder resin in addition to the resin (B1) having an aromatic carboxyl group.

[0160] The resin (B2) not having an aromatic carboxyl group is not particularly limited as long as it is a resin not having an aromatic carboxyl group as an acidic group, and a known resin can be used. For example, (meth) acrylic resin, styrene / (meth) acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamide-imide resin, cyclic olefin resin, etc. can be mentioned.

[0161] From the viewpoint of film resistance after low-temperature heating, the resin (B2) without an aromatic carboxyl group is more preferably a resin having a monomer unit containing a thermally crosslinkable group and a monomer unit containing an acidic group (however, excluding a monomer unit containing an aromatic carboxyl group). The thermally crosslinkable group is a group that undergoes crosslinking by a crosslinking reaction caused by heating. For example, a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, a tertiary alkyl group, etc. can be cited.

[0162] The resin having monomer units other than thermally crosslinkable groups and monomer units other than aromatic carboxyl groups containing acidic groups is synthesized by, for example, copolymerizing monomers other than thermally crosslinkable groups, monomers other than aromatic carboxyl groups containing acidic groups, and other arbitrarily copolymerizable monomers.

[0163] From the viewpoint of storage stability and resistance after low-temperature heating, the monomer unit containing a thermally crosslinkable group is preferably formed from a monomer represented by the following general formulae (7) to (11).

[0164]

Chemistry 6

[0165] General formula (7)

[0166]

[0167] In the general formula (7), R 1 represents a hydrogen atom or a methyl group.

[0168] In the general formula (7), R 2 and R 3 Each independently represents an alkyl group having 1 to 10 carbon atoms.

[0169] The alkyl group having 1 to 10 carbon atoms may be any of a linear, branched, or combination thereof. For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, etc. are mentioned. Among them, methyl, ethyl, and n-propyl are preferred.

[0170] In general formula (7), L 1 It represents a single bond or a divalent organic group.

[0171] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms and a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms.

[0172] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof. For example, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. are mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0173] In general formula (7), L 2 represents a single bond or an oxygen atom.

[0174] In general formula (7), L 3 and L 4 Each independently represents a single bond or a divalent organic group.

[0175] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms.

[0176] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof alkyl group. For example, methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylidene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. may be mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0177] The method for producing the monomer represented by the general formula (7) is not particularly limited, and a known method may be used. For example, methods described in Japanese Unexamined Patent Publication No. 10-316643 and International Publication No. 2022 / 145298 may be mentioned.

[0178] The following are compounds of formulae (7-1) to (7-10) as specific examples of the monomer represented by general formula (7). However, the present invention is not limited to these.

[0179]

Chemistry 7

[0180]

[0181] From the viewpoint of resistance after low-temperature heating, the monomer represented by general formula (7) is preferably one or more compounds selected from the above-mentioned formulas (7-1), (7-2), (7-3), (7-4), (7-9) and (7-10).

[0182] The monomer represented by the general formula (7) can be used alone or in combination of two or more.

[0183]

Chemistry 8

[0184] General formula (8)

[0185]

[0186] In the general formula (8), R 1 represents a hydrogen atom or a methyl group.

[0187] In the general formula (8), R 4 ~R 6 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

[0188] The alkyl group having 1 to 10 carbon atoms may be any of a linear, branched, or combination thereof. For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, etc. may be mentioned. 4 and R 5 Preferably, a hydrogen atom, R 6 Preferred are methyl, ethyl and n-propyl.

[0189] In the general formula (8), L 1 It represents a single bond or a divalent organic group.

[0190] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms and a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms.

[0191] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof. For example, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. are mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0192] The method for producing the monomer represented by the general formula (8) is not particularly limited, and a known method can be used. For example, the method described in International Publication No. 2022 / 145298 can be mentioned.

[0193] As specific examples of the monomer represented by the general formula (8), compounds of the following formulas (8-1) to (8-6) are shown. However, the present invention is not limited to these.

[0194]

Chemistry 9

[0195]

[0196] The monomer represented by the general formula (8) can be used alone or in combination of two or more.

[0197]

Chemistry 10

[0198] General formula (9)

[0199]

[0200] In the general formula (9), R 1 represents a hydrogen atom or a methyl group.

[0201] In the general formula (9), R 7 It represents an alkyl group having 1 to 10 carbon atoms.

[0202] The alkyl group having 1 to 10 carbon atoms may be any of a linear, branched, or combination thereof. For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, etc. are mentioned. Among them, methyl, ethyl, and n-propyl are preferred.

[0203] In the general formula (9), L 1 It represents a single bond or a divalent organic group.

[0204] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms and a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms.

[0205] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof. For example, methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. are mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0206] The method for producing the monomer represented by the general formula (9) is not particularly limited, and a known method may be used, for example, the method described in Coatings Technology, Vol. 62, by Witzeman, JS and Dell Rector, FJ.

[0207] The following are compounds of formula (9-1) to formula (9-4) as specific examples of the monomer represented by general formula (9). However, the present invention is not limited to these.

[0208]

Chemistry 11

[0209]

[0210] The monomer represented by the general formula (9) can be used alone or in combination of two or more.

[0211]

Chemistry 12

[0212] General formula (10)

[0213]

[0214] In the general formula (10), R 1 represents a hydrogen atom or a methyl group.

[0215] In the general formula (10), R 8 ~R 10 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. 8 ~R 10 At least one of them is an alkoxy group having 1 to 6 carbon atoms.

[0216] Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, butyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, and isobutyl.

[0217] Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, and an isopropoxy group. Among them, a methoxy group and an ethoxy group are preferred from the viewpoint of resistance after low-temperature heating.

[0218] From the viewpoint of resistance after low-temperature heating, it is preferred that in the general formula (10), R 8 ~R 10 At least two of them are alkoxy groups having 1 to 6 carbon atoms.

[0219] In the general formula (10), L 1 It represents a single bond or a divalent organic group.

[0220] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms and a group having -O- between carbon-carbon bonds of an alkylene group having 1 to 20 carbon atoms.

[0221] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof. For example, methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylidene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. may be mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0222] As specific examples of the monomer represented by the general formula (10), compounds of the following formulas (10-1) to (10-6) are shown. However, the present invention is not limited to these.

[0223]

Chemistry 13

[0224]

[0225] Examples of commercially available products of the monomer represented by the general formula (10) include KBM-502, 503, 5103, 5803, KBE-502, and 503 manufactured by Shin-Etsu Silicone Co., Ltd.

[0226] The monomer represented by the general formula (10) can be used alone or in combination of two or more.

[0227]

Chemistry 14

[0228] General formula (11)

[0229]

[0230] In the general formula (11), R 1 represents a hydrogen atom or a methyl group.

[0231] In the general formula (11), R 11 ~R 13 Each independently represents an alkyl group having 1 to 10 carbon atoms.

[0232] The alkyl group having 1 to 10 carbon atoms may be any of a linear, branched, or combination thereof. For example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, etc. are mentioned. Among them, methyl is preferred.

[0233] In the general formula (11), L 1 It represents a single bond or a divalent organic group.

[0234] Examples of the divalent organic group include an alkylene group having 1 to 20 carbon atoms, a group having -NH-, and a combination thereof.

[0235] The alkylene group having 1 to 20 carbon atoms may be any of a linear, branched or combination thereof. For example, methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylidene, 2-methylpropylene, 2-methylhexylene, tetramethylethylene, etc. may be mentioned. Among them, methylene, ethylene and n-propylene are preferred.

[0236] The following are compounds of formula (11-1) to formula (11-6) as specific examples of the monomer represented by general formula (11). However, the present invention is not limited to these.

[0237]

Chemistry 15

[0238]

[0239] The monomer represented by the general formula (11) can be used alone or in combination of two or more.

[0240] From the viewpoint of storage stability and resistance after low-temperature heating, the monomer unit containing a thermally crosslinkable group is more preferably formed from one or more of the monomer represented by the general formula (7) and the monomer represented by the general formula (8).

[0241] The monomer unit containing a thermally crosslinkable group can be formed by using the monomers represented by the general formula (7) to (11) alone or in combination of two or more.

[0242] The monomer unit containing a thermally crosslinkable group may be a combination of a monomer unit formed from a monomer represented by the general formula (7) to (11) and a monomer unit formed from a monomer other than the monomer represented by the general formula (7) to (11).

[0243] Examples of monomers other than the monomers represented by the general formulae (7) to (11) include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-9-yl(meth)acrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino](meth)acrylate ethyl, 2-[o-(1'-methylpropyleneamino)carboxyamino](meth)acrylate ethyl, and the like.

[0244] The content of the monomer unit containing a thermally crosslinkable group is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, based on the total monomer units of the resin, from the viewpoint of storage stability and resistance after low-temperature heating.

[0245] Examples of monomers containing an acidic group (except monomers having an aromatic carboxyl group) include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethylsuccinic acid, 2-acryloyloxyethylhexyl hydrogenated phthalic acid, ethylene sulfonic acid, 2-acrylamide-2-methylpropane sulfonic acid, tert-butylacrylamidesulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0246] The acidic group-containing monomer may be used alone or in combination of two or more.

[0247] In addition to the method of copolymerizing a monomer containing a thermally crosslinkable group and a monomer containing an acidic group, the method of adding an acid anhydride (modified compound) to the hydroxyl group contained in the resin (precursor) can also be used as a method of introducing an acid group. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and the like.

[0248] The content of the acidic group-containing monomer unit is preferably 1 mol% to 40 mol%, more preferably 5 mol% to 30 mol%, based on the total structural units of the resin.

[0249] The monomer unit other than the monomer unit containing a thermally crosslinkable group and the monomer unit containing an acidic group (hereinafter, referred to as other monomer unit) may be contained.

[0250] Other monomer units include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, and (meth)acrylate. Dicyclopentenyloxyethyl acrylate, adamantyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, EO-modified (meth)acrylate of phenol, EO- or PO-modified (meth)acrylate of nonylphenol Acrylates, EO or PO modified (meth)acrylates of p-cumylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, vinyl acetate or vinyl propionate, phenylmaleimide, methyl Maleimide, ethylmaleimide, 1,2-bismaleimide ethane-1,6-bismaleimide hexane, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrene) maleimide, N-(2,4,6-trichlorophenyl) maleimide, N-(4-aminophenyl) maleimide, N-(4-nitrophenyl) maleimide, N-benzyl maleimide, N-bromomethyl-2,3-Dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, dimethyl-2,2'-[oxybis( bis(methylene)] bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)] bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)] bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)] bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)] bis-2-acrylate, etc.

[0251] The acid value of the resin (B2) having no aromatic carboxyl group is preferably 20 to 200 mgKOH / g, more preferably 30 to 180 mgKOH / g.

[0252] The weight average molecular weight of the resin (B2) having no aromatic carboxyl group is preferably 3,000 to 50,000, more preferably 3,000 to 20,000.

[0253] The resin (B2) having no aromatic carboxyl group can be used alone or in combination of two or more.

[0254] From the viewpoint of resistance after low-temperature heating, the content of the resin (B2) having no aromatic carboxyl group is preferably 30% by mass to 95% by mass in 100% by mass of the resin (B) having an acidic group.

[0255] [Polymerizable compound (C)]

[0256] Examples of the polymerizable compound (C) include monomers and oligomers having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group having an ethylenically unsaturated double bond, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

[0257] The polymerizable compound (C) may be a known compound, and examples thereof include a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a hydroxyl group, a polymerizable compound (C3) having a dendritic structure or a hyperbranched structure, a polymerizable compound (C4) having an acidic group, a polymerizable compound (C5) having a urethane bond, a lactone-modified polymerizable compound (C6), and other polymerizable compounds (C7).

[0258] The polymerizable compound (C) can be used alone or in combination of two or more.

[0259] The content of the polymerizable compound (C) is preferably 1 to 80% by mass, more preferably 5 to 70% by mass, in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0260] (Polymerizable compound (C1) having an amine structure)

[0261] The amine structure possessed by the polymerizable compound (C1) having an amine structure may include primary amines, secondary amines, and tertiary amines. Among them, secondary amines and tertiary amines are preferred. However, the amine structure possessed by the polymerizable compound (C1) having an amine structure does not include an amide structure, an imide structure, and a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0262] Examples of the polymerizable compound (C1) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of a (meth)acrylate compound (X) and an amine compound (Y).

[0263] Examples of the (meth)acrylate compound (X) include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipropylene tri(meth)acrylate, dipropylene tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri- and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri- and tetra(meth)acrylate, dipropylene oxide-modified tri- and tetra(meth)acrylate, dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate, and the like.

[0264] Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and propene oxide.

[0265] Moreover, as a (meth)acrylate compound (X), the (meth)acrylate compound which has an acidic group is mentioned.

[0266] The (meth)acrylate compound (X) can be used alone or in combination of two or more.

[0267] Examples of the amine compound (Y) include primary amines such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, and p-aminophenol;

[0268] Secondary amines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-methylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, 4-anilinephenol, etc.

[0269] The amine compound (Y) can be used alone or in combination of two or more.

[0270] The method for producing the Michael addition reaction product of the (meth)acrylate compound (X) and the amine compound (Y) is not particularly limited, and a known method can be used. For example, methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be cited.

[0271] The polymerizable compound (C1) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of methods for introducing an acidic group and / or a hydroxyl group include a method of using a compound having an acidic group and / or a hydroxyl group for the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after the Michael addition reaction.

[0272] Examples of commercially available products of the polymerizable compound (C1) having an amine structure include ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel Zenshin Co., Ltd., and CN371NS, 372, 374, 383, and 386 manufactured by Arkema.

[0273] The polymerizable compound (C1) having an amine structure may have a urethane bond. Thus, a physical crosslinking structure based on intermolecular hydrogen bonds between urethane bonds, urethane bonds and functional groups of the substrate is formed together with a chemical crosslinking structure based on polymerization. The molecular cohesion energy possessed by the intermolecular hydrogen bonds of the urethane bonding portion is greater than the cohesion energy possessed by other organic structures such as ether bonds. Thus, it is inferred that the film becomes soft and firm through the interaction between the urethane bonds, and the tolerance is improved.

[0274] The method of introducing urethane bonds can be carried out, for example, by urethane reaction of a Michael addition reaction product (precursor) of the above-mentioned (meth)acrylate compound (X) and the above-mentioned amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0275] Examples of the polyisocyanate compound (Z) include polyisocyanate compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.

[0276] Polyisocyanate compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate methyl)cyclohexane;

[0277] Polyisocyanate compounds having an aromatic structure such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, bischloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene.

[0278] In addition, biuret forms, isocyanurate forms, adducts, allophanate forms, and the like of these compounds can be mentioned.

[0279] The polyisocyanate compound (Z) can be used alone or in combination of two or more.

[0280] The method of the urethane reaction of the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in Japanese Patent Table No. 2018-517797 can be cited.

[0281] (Polymerizable compound (C2) having a hydroxyl group)

[0282] Examples of the polymerizable compound (C2) having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, isocyanate, Acrylates such as EO or PO modified (meth)acrylates with uric acid, EO or PO modified di(meth)acrylates with isocyanuric acid, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, epoxy(meth)acrylates obtained by reacting the epoxy group of a compound having an epoxy group with the carboxyl group of (meth)acrylic acid, etc. Among them, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0283] Examples of commercially available products of the polymerizable compound (C2) having a hydroxyl group include KAYARA DR-128H and R-167 manufactured by Nippon Kayaku Co., Ltd., ARONIX M-5700 and M-920 manufactured by Toagosei Co., Ltd., NK ESTER 701A manufactured by Shin-Nakamura Chemical Co., Ltd., LIGHT ESTER HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P manufactured by Kyoeisha Chemical Co., Ltd., epoxy esters M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A, and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0284] (Polymerizable compound (C3) having a dendritic structure or a hyperbranched structure)

[0285] The compound having a dendritic structure has a chemical structure in which branches are regularly repeated from a chemical structure constituting a core (hereinafter also referred to as a core part) to the outside thereof and a polymerizable unsaturated group is bonded to the terminal thereof, and has a highly controlled chemical structure and molecular weight in a spherical shape. The hyperbranched structure has a chemical structure similar to the dendritic structure.

[0286] Examples of commercially available products of the polymerizable compound (C3) having a dendritic structure or a hyperbranched structure include VISCOAT#1000LT (dendritic structure, average number of acryloyl groups: 14), SIRUS-501 (dendritic structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendritic structure, average number of acryloyl groups: 18), SP-1108 (dendritic structure, average number of acryloyl groups: 13) manufactured by Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average number of acryloyl groups: 9), CN2302 (hyperbranched structure, average number of acryloyl groups: 16), CN2303 (hyperbranched structure, average number of acryloyl groups: 6), CN2304 (hyperbranched structure, average number of acryloyl groups: 18) manufactured by Sartomer Co., Ltd., and Eternal Materials Co., Ltd. Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), 6363 (hyperbranched structure, average number of acryloyl groups: 16), DR-E522 (hyperbranched structure, average number of acryloyl groups: 15) manufactured by CERT Materials Co., Ltd.

[0287] (Polymerizable compound having an acidic group (C4))

[0288] The polymerizable compound (C4) having an acidic group is a compound having a molecular weight of 100 or more, and examples thereof include esters of polyvalent alcohols, poly(meth)acrylates containing free hydroxyl groups of (meth)acrylic acid, and dicarboxylic acids; esters of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc.

[0289] Examples of the polyvalent alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerol, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0290] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0291] Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid.

[0292] Examples of the monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0293] Examples of commercially available products of the polymerizable compound (C4) having an acidic group include Aronix M-5300, M-5400, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd. and β-CEA manufactured by Daicel Zenshin Co., Ltd.

[0294] (Polymerizable compound (C5) having urethane bond)

[0295] Examples of the polymerizable compound (C5) having a urethane bond include urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and urethane (meth)acrylates obtained by reacting a polyfunctional isocyanate with a polyvalent alcohol and further reacting a hydroxyl group-containing (meth)acrylate.

[0296] Examples of the hydroxyl group-containing (meth)acrylate 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 (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxyl (meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0297] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as toluene diisocyanate, diphenylmethylene diisocyanate, and xylylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate; biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0298] The polymerizable compound (C5) having a urethane bond may have an acidic group. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group. Among them, a carboxyl group is preferred.

[0299] The method of introducing an acidic group into the polymerizable compound (C5) having a urethane bond can be synthesized by, for example, first reacting the above-mentioned hydroxyl-containing (meth)acrylate with the above-mentioned polyfunctional isocyanate and then adding a mercapto compound having a carboxyl group to the product.

[0300] Examples of the mercapto compound having a carboxyl group include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0301] Commercially available products of the polymerizable compound (C5) having a urethane bond include, for example, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001g manufactured by Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 manufactured by Daicel Corporation.

[0302] (Lactone-modified polymerizable compound (C6))

[0303] The lactone-modified polymerizable compound (C6) is a compound having a structure modified with lactone in the molecule. The lactone-modified polymerizable compound (C6) is obtained by esterifying a polyvalent alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0304] Examples of commercially available products of the lactone-modified polymerizable compound (C6) include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0305] (Other polymerizable compounds (C7))

[0306] Examples of other polymerizable compounds (C7) include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (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 EO or PO modified tri(meth)acrylate, isocyanate, (Meth)acrylates such as EO or PO modified tri(meth)acrylate of cyanuric acid, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO or PO modified hexa(meth)acrylate, tricyclodecyl (meth)acrylate, (meth)acrylate of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0307] Examples of commercially available products of other polymerizable compounds (C7) include KAYARADNPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, D-310 manufactured by Nippon Kayaku Co., Ltd., and ARONIX manufactured by Toagosei Co., Ltd. M-101A, M-102, M-111, M-113, M-120, M-140, M-208, M-211B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, VISCOAT #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 manufactured by Osaka Gas Chemical Co., Ltd. OGSOL EA-0200, EA-0300 manufactured by Miwon Specialty Chemical Co., Ltd. Miramer HR6060, 6100, 6200, NK ESTER A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP, etc. manufactured by Shin-Nakamura Chemical Industry Co., Ltd.

[0308] In addition, (meth)acrylates having a hydroxyl group and an acidic group, (meth)acrylates having a hydroxyl group and a urethane bond, and lactone-modified (meth)acrylates having a hydroxyl group may be mentioned.

[0309] From the viewpoint of resistance after low-temperature heating, the polymerizable compound (C) preferably contains one or more selected from the group consisting of a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a hydroxyl group, and a polymerizable compound (C3) having a dendritic structure or a hyperbranched structure.

[0310] The total content of the polymerizable compound (C1) having an amine structure, the polymerizable compound (C2) having a hydroxyl group, and the polymerizable compound (C3) having a dendritic structure or a hyperbranched structure is preferably 10% by mass to 100% by mass, and more preferably 20% by mass to 100% by mass in 100% by mass of the polymerizable compound (C).

[0311] [Polymerization initiator (D)]

[0312] Examples of the polymerization initiator (D) include compounds that generate radicals by the action of light or heat to initiate or promote radical polymerization reaction.

[0313] The polymerization initiator that generates radicals by light (hereinafter referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light in the ultraviolet light region to the visible light region.

[0314] The polymerization initiator that generates radicals by heat (hereinafter referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0315] Examples of the photopolymerization initiator include acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylmercapto)phenyl]-2-morpholinopropane-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone.

[0316] 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-phenylvinyl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxyphenylvinyl)-6-triazine and other triazine compounds;

[0317] Oxime compounds such as 1-[4-(phenylthio)phenyl-1,2-octanedione 2-(O-benzoyl oxime)], 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethanone 1-(O-acetyl oxime);

[0318] Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide;

[0319] Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds, etc.

[0320] Among the commercially available products, there can be mentioned acetophenone compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF JAPAN, ADEKA ARKLS N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, and TRONLYTR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057, and IGM manufactured by Changzhou Qiangli New Materials Co., Ltd. Omnirad 1312, 1314, 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by SAMYANG CORPORATION, DFI-020, 306, EOX-01 manufactured by DAITOCHEMIX, etc. In addition, compounds described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, International Publication No. 2015 / 036910, JP-T-2019-507108, JP-T-2019-528331, International Publication No. 2021 / 175855, JP-T-2022-5115524, and International Publication No. 2023 / 085056 can also be mentioned.

[0321] As the thermal polymerization initiator, for example, benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsilyloxy)-1,1,2,2-tetra(4-methoxyphenyl)ethane, Pinacol compounds such as tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane;

[0322] The azo compounds and organic peroxides already described can also be used.

[0323] The polymerization initiator (D) can be used alone or in combination of two or more.

[0324] The content of the polymerization initiator (D) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, in 100% by mass of the nonvolatile components of the red photosensitive composition.

[0325] (The absorption coefficient of light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate is 5.0×10 3 L / mol·cm or more polymerization initiator (D1)

[0326] The red photosensitive composition of the present invention contains propylene glycol monomethyl ether acetate, and the extinction coefficient of light with a wavelength of 365 nm is 5.0×10 3 As the polymerization initiator (D), a polymerization initiator (D1) having an amount of at least L / mol·cm (hereinafter, also referred to as the polymerization initiator (D1)) is used.

[0327] The extinction coefficient of the polymerization initiator (D1) for light of wavelength 365 nm in propylene glycol monomethyl ether acetate is preferably 5.0×10 3 L / mol·cm~5.0×10 4 L / mol·cm, more preferably 1.0×10 4 L / mol·cm~4.0×10 4 L / mol·cm.

[0328] The polymerization initiator (D1) is not particularly limited, and known compounds can be used. For example, compounds described in International Publication No. 2008 / 078678, Japanese Patent Publication No. 2009-134289, Japanese Patent No. 4600600, Japanese Patent Publication No. 2011-132215, Japanese Patent Table No. 2014-500852, Japanese Patent Table No. 2015-523318, International Publication No. 2015 / 036910, International Publication No. 2017 / 051680, International Publication No. 2021 / 175855, Japanese Patent Table No. 2022-515524, etc. can be cited.

[0329] Specific examples of the polymerization initiator (D1) are shown below, but the present invention is not limited to these.

[0330]

Chemistry 16

[0331]

[0332]

Chemistry 17

[0333]

[0334] The polymerization initiator (D1) can be used alone or in combination of two or more.

[0335] The content of the polymerization initiator (D1) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, in 100% by mass of the polymerization initiator (D).

[0336] (Polymerization initiator (D2) represented by general formula (18))

[0337] The polymerization initiator (D1) may contain a polymerization initiator (D2) represented by the general formula (18) (hereinafter, referred to as the polymerization initiator (D2)). The polymerization initiator (D2) has a high free radical generating ability and is not easily inhibited by oxygen. Therefore, photocuring is performed and the resistance under low temperature heating is further improved.

[0338]

Chemistry 18

[0339] General formula (18)

[0340]

[0341] In the general formula (18), R1 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclicoxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. Among them, an alkyl group is preferred from the viewpoint of synthesis and the characteristics of the red photosensitive composition.

[0342] In the general formula (18), R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group. Among them, an alkyl group substituted with an alkyl group having 3 to 10 carbon atoms or a cycloalkyl group is preferred from the viewpoint of synthesis and the characteristics of the red photosensitive composition.

[0343] In the general formula (18), R4 and R5 each independently represent a hydrogen atom, a halogen atom, a cyano group or a nitro group.

[0344] The hydrogen atom of the substituent in the above-mentioned R1 to R3 may be further substituted by other substituents. Examples of the other substituents include halogen groups such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, alkoxy groups such as methoxy groups, ethoxy groups, and tert-butoxy groups, aryloxy groups such as phenoxy groups and p-tolyloxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups, butoxycarbonyl groups, and phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, and benzoyloxy groups, acyl groups such as acetyl groups, benzoyl groups, isobutyryl groups, acyl groups such as methacryloyl groups, methacryloyl groups, and methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups, and alkyl groups such as methylamino groups and cyclohexylamino groups. amino, dimethylamino, diethylamino, morpholinyl, piperidinyl and other dialkylamino, phenylamino, p-tolylamino and other arylamino, methyl, ethyl, tert-butyl, dodecyl and other alkyl, phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthracenyl, phenanthryl and other aryl, furyl, thienyl and other heterocyclic groups, and hydroxyl, carboxyl, formyl, mercapto, sulfonic acid, methylsulfonyl, p-toluenesulfonyl, amino, nitro, cyano, trifluoromethyl, trichloromethyl, trimethylsilyl, phosphinico, phosphono, trimethylammonium, dimethylsulfonium, triphenylphenacylphosphonium and the like.

[0345] Specific examples of the polymerization initiator (D2) are shown below, but the present invention is not limited to these.

[0346]

Chemistry 19

[0347]

[0348] [Thermal crosslinking compound (E)]

[0349] From the viewpoint of resistance after low-temperature heating, the red photosensitive composition of the present invention preferably contains a heat-crosslinkable compound (E). Thus, the heat-crosslinkable compound (E) is crosslinked by heating, and the resistance is improved. In addition, in this specification, the heat-crosslinkable compound (E) does not have an acidic group and a polymerizable unsaturated group, and is therefore different from the resin (B) and the polymerizable compound (C) having an acidic group.

[0350] As the heat-crosslinkable compound (E), any known compound can be used as long as it is a compound having a heat-crosslinkable group. For example, compounds having an epoxy group, compounds having a blocked isocyanate group, compounds having an oxetane group, compounds having a hydroxymethyl group, compounds having a phenol group, compounds having an alkoxyalkyl group, etc. can be cited. Among them, it is preferred to include one or more selected from the group consisting of compounds having an epoxy group and compounds having a blocked isocyanate group.

[0351] The heat-crosslinkable compound (E) can be used alone or in combination of two or more.

[0352] The content of the heat-crosslinkable compound (E) is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0353] (Compound (E1) having an epoxy group)

[0354] The heat-crosslinkable compound (E) preferably contains a compound (E1) having an epoxy group. This allows the epoxy group to be crosslinked by heating, thereby further improving the resistance.

[0355] The epoxy group is a group having a 3-membered ring cyclic ether structure, and also includes an alicyclic epoxy group. Examples of compounds having an epoxy group include polyglycidyl ether compounds of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and hydrogenated bisphenol F diglycidyl ether;

[0356] Polyglycidyl ether compounds of polyvalent alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether;

[0357] Polyglycidyl ether compounds of polyether polyols prepared by adding alkylene oxide to polyvalent alcohols such as ethylene glycol, propylene glycol, and glycerol;

[0358] 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl- Compounds having two or more 3,4-epoxycyclohexyl groups in the molecule, such as 5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalic acid dioctyl ester, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone;

[0359] 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol, and the like.

[0360] Examples of commercially available products of the compound (E1) having an epoxy group include EPICOAT 807, 815, 825, 827, 828, 190P, and 191P manufactured by Shell EPOXY, TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, and 1020 manufactured by Nippon Kayaku Co., Ltd. EPICOAT 1004, 1256, JER 1032H60, 157S65, 157S70, 152, and 154 manufactured by Japan EPOXY RESINS, CELOXIDE 2021, EHPE-3150, and EPOLEAD GT401 manufactured by Daicel Chemical Industries, Ltd., and DENACOL manufactured by Nagase Chemtex. EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, TEPIC-L, H, S manufactured by Nissan Chemical Industries, EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc. manufactured by DIC.

[0361] The compound (E1) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0362] The epoxy equivalent of the compound (E1) having an epoxy group is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of the compound having an epoxy group containing 1 equivalent of an epoxy group.

[0363] From the viewpoint of resistance after low-temperature heating, the compound (E1) having an epoxy group more preferably includes a compound represented by the following general formula (12).

[0364]

Chemistry 20

[0365] General formula (12)

[0366]

[0367] In the general formula (12), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0368] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol.

[0369] The group obtained by removing m hydroxyl groups from an m-valent alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be a linear, branched, or cyclic group or a group bonded thereto. Examples of the alkyl group having 2 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, 2,2-dimethylpropyl, butyl, isobutyl, tert-butyl, 3,3-dimethylbutyl, pentyl, isopentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl. Among them, branched alkyl groups having 3 to 12 carbon atoms are more preferred.

[0370] m represents an integer of 1-6, and n represents an integer of 1-30.

[0371] When m is 2 or more, n in each bracketed group in the general formula (12) may be the same or different.

[0372] Examples of the compound represented by the general formula (12) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adducts of 2,2-bis(hydroxymethyl)-1-butanol. Examples of commercially available products include EHPE-3150 and EHPE-3150CE manufactured by DAICEL.

[0373] The acid value of the compound (E1) having an epoxy group is preferably 10 mgKOH / g or less.

[0374] The compound (E1) having an epoxy group can be used alone or in combination of two or more.

[0375] The content of the compound (E1) having an epoxy group is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, in 100% by mass of the heat-crosslinkable compound (E).

[0376] (Compound having a blocked isocyanate group (E2))

[0377] The heat-crosslinkable compound (E) preferably contains a compound (E2) having a blocked isocyanate group.

[0378] The compound (E2) having a blocked isocyanate group is a compound having an isocyanate group protected by a blocking agent. The debonding temperature of the blocking agent for blocking the isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0379] The compound (E2) having a blocked isocyanate group is synthesized by reacting a compound having an isocyanate group with a blocking agent by a known method, for example, methods described in Japanese Patent Application Laid-Open No. 52-116420, Japanese Patent Application Laid-Open No. 60-149572, Japanese Patent Application Laid-Open No. 7-31953, Japanese Patent Application Laid-Open No. 10-306136, Japanese Patent Application Laid-Open No. 2012-012567, etc.

[0380] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, thiol compounds, imidazole compounds and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, pyrazole compounds, and active methylene compounds are particularly preferred from the viewpoint of resistance after low-temperature heating. The desorption temperature of the active methylene compound or the temperature of the transesterification reaction is as low as 80°C to 110°C, and the reaction can be fully performed even at low temperatures, thereby improving resistance.

[0381] Examples of the compound having an isocyanate group include compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate.

[0382] Compounds having an alicyclic structure such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane;

[0383] Compounds having an aromatic structure such as 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, benzenedimethylene diisocyanate, m-tetramethylbenzenedimethylene diisocyanate, 4,4-diphenylmethane diisocyanate, toluene diisocyanate, dichloromethyldiphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene. In addition, biuret bodies, isocyanurate bodies, adducts, urethane-formate bodies of these compounds, and reaction products of these compounds and polyols can be cited.

[0384] The compound having an isocyanate group is preferably a biuret body, isocyanurate body, adduct, or urethane-formate body of a compound having an aliphatic structure or an alicyclic structure.

[0385] Examples of the compound having a blocked isocyanate group (E2) include the following compounds. In the following structural formulas, X represents a blocked isocyanate group. In addition, the present invention is not limited to these.

[0386]

Chemical formula 21

[0387]

[0388] The X (blocked isocyanate group) of the above compounds can be, for example, the structures shown in the following (X-1) to (X-8). In the following structures, * represents a bonding portion. In addition, the present invention is not limited to these.

[0389]

Chemical formula 22

[0390]

[0391] Among the above structures, from the viewpoints of storage stability and solvent resistance after low-temperature heating, (X-1), (X-4), (X-6), (X-7), and (X-8) are preferred, (X-1) and (X-8) are more preferred, and (X-1) is further preferred.

[0392] Examples of commercially available products of the compound (E2) having a blocked isocyanate group and having an aliphatic structure include DURANATE SBN-70D, SBB-70P, SBF-70E, TPA-B80E, 17B-60P, MF-B60B, E402-B80B, MF-K60B, and WM44-L70G manufactured by Asahi Kasei Corporation, TAKENATE B-882 manufactured by Mitsui Chemicals, and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.

[0393] Examples of the compound having an alicyclic structure include TAKENATE B-846N manufactured by Mitsui Chemicals, CORONATE BI-301, 2507, 2554 manufactured by Tosoh Corporation, BI7950, BI7951, BI7990 manufactured by Baxenden Chemical Co., Ltd., and the like;

[0394] Examples of the compound having an aromatic structure include TAKENATE B-830 and B-815N manufactured by Mitsui Chemicals, Inc.

[0395] The number of blocked isocyanate groups in the compound (E2) having a blocked isocyanate group is preferably 1 to 20, more preferably 2 to 15.

[0396] The weight average molecular weight of the compound (E2) having a blocked isocyanate group is preferably 300 to 5,000, more preferably 500 to 3,000.

[0397] The acid value of the compound (E2) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0398] The compound (E2) having a blocked isocyanate group can be used alone or in combination of two or more.

[0399] The content of the compound (E2) having a blocked isocyanate group is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, in 100% by mass of the heat-crosslinkable compound (E).

[0400] As the heat-crosslinkable compound (E), it is more preferable to use in combination a compound (E1) having an epoxy group and a compound (E2) having a blocked isocyanate group from the viewpoint of resistance after low-temperature heating.

[0401] The mass ratio of the compound (E1) having an epoxy group to the compound (E2) having a blocked isocyanate group is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 30:70 to 70:30.

[0402] [Ultraviolet absorber (F)]

[0403] From the viewpoint of pattern formation, the red photosensitive composition of the present invention preferably contains an ultraviolet absorber (F), thereby suppressing the influence of changes in exposure amount and the type and amount of polymerization initiator, and obtaining a stable pattern width.

[0404] Examples of the ultraviolet absorber (F) include benzophenone compounds, benzotriazole compounds, triazine compounds, conjugated diene compounds, methyl dibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, salicylate compounds, etc. Among them, benzophenone compounds are preferably included.

[0405] Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid trihydrate, 2-hydroxy-4-octyloxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, diethylaminohydroxybenzoyl hexyl benzoate, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Examples of commercially available products include UVINUL A, 3049, 3050, and UVA-935LH manufactured by BASF JAPAN, and ADKSTAB1413 manufactured by ADEKA.

[0406] Among them, 2,2',4,4'-tetrahydroxybenzophenone and 4,4'-bis(diethylamino)benzophenone are preferred.

[0407] Examples of commercially available products of the benzotriazole compound include TINUVIN PS, 99-2, 326, 384-2, 900, 928, 970, 1130, and UVA-903KT manufactured by BASF Japan and ADKSTAB LA-31RG and LA-31G manufactured by ADEKA.

[0408] As commercially available products of the triazine compound, for example, TINUVIN 400, 405, 406, 477, and 479 manufactured by BASF Japan, and ADKSTAB LA-46 and LA-F70 manufactured by ADEKA Corporation may be mentioned.

[0409] Examples of the conjugated diene compound include UV503 manufactured by Daito Chemical Co., Ltd.

[0410] Examples of the methyl dibenzoyl compound include 1,3-diphenyl-1,3-propanedione, 1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-1,3-propanedione, and 1,3-bis(4-methoxyphenyl)-1,3-propanedione.

[0411] The ultraviolet absorber (F) can be used alone or in combination of two or more.

[0412] It is preferable that content of the ultraviolet absorber (F) is 0.1 mass % - 5 mass % in 100 mass % of the non-volatile components of a red photosensitive composition.

[0413] [Alkaline pigment derivative (G)]

[0414] The red photosensitive composition of the present invention preferably contains a basic pigment derivative (G), whereby the dispersion stability of the color material (A) is further improved.

[0415] Examples of the basic pigment derivative (G) include compounds having a structure in which a part of a compound having a pigment structure is substituted with a basic group.

[0416] Examples of compounds having a pigment structure include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, pyrene compounds, perylene compounds, thiazine indigo compounds, triazine compounds, benzimidazolone compounds, benzisoindole compounds, isoindoline compounds, isoindolinone compounds, quinophthalone compounds, naphthol compounds, squarylium compounds, threne compounds, naphthalocyanine compounds, azomethine compounds, pyrrolopyrrole compounds, azo compounds, thioindigo compounds, etc. Among them, diketopyrrolopyrrole compounds, anthraquinone compounds, benzisoindole compounds, isoindoline compounds, and quinophthalone compounds are preferred, and benzisoindole compounds and quinophthalone compounds are more preferred.

[0417] Examples of the basic group include amino groups, pyridyl groups and salts thereof, and salts of ammonium groups. Examples of the compound that forms a salt include hydroxide ions, halogen ions, carboxylic acid ions, and sulfonic acid ions.

[0418] The basic pigment derivative (G) is preferably added during the refinement of the color material (A) or the dispersion treatment of the color material (A). The average primary particle size of the basic pigment derivative (G) is preferably 5 nm to 200 nm.

[0419] The basic pigment derivative (G) can be used alone or in combination of two or more.

[0420] The content of the basic pigment derivative (G) is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, based on 100 parts by mass of the color material (A).

[0421] As the basic pigment derivative (G), it is preferred to use one or more of a compound represented by the following general formula (13) and a compound represented by the following general formula (14).

[0422]

Chemistry 23

[0423] General formula (13)

[0424]

[0425] In the general formula (13), R1 represents a group represented by the following general formula (15).

[0426] In the general formula (13), R2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

[0427] The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, etc. may be mentioned.

[0428] In the general formula (13), R3 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, or a group represented by -NR4R5 (R4 and R5 are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

[0429]

Chemistry 24

[0430] General formula (15)

[0431]

[0432] In the general formula (15), X represents a single bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC6H4CO- or -CONHC6H4-.

[0433] In the general formula (15), R6 and R7 each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a group in which R6 and R7 form a heterocyclic ring.

[0434] The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, etc. may be mentioned.

[0435] Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, etc. The aryl group may be substituted with a halogen atom, an amino group, a nitro group, or the like.

[0436] In the general formula (15), n represents an integer of 0-20.

[0437]

Chemistry 25

[0438] General formula (14)

[0439]

[0440] In the general formula (14), R8 represents a group represented by the general formula (16).

[0441] In the general formula (14), R9 to R 12 Each independently represents a hydrogen atom or a halogen atom.

[0442]

Chemistry 26

[0443] General formula (16)

[0444]

[0445] In the general formula (16), Y1 represents a single bond, -NR 14 SO2-、-SO2NR 14 -、-CONR 14 -、-NR 14 CO- or -CH2NR 14 COCH2NR 14 -.

[0446] R 14 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

[0447] In the general formula (16), Y2 represents a single bond, an arylene group or an aromatic ring, which can be selected from -NR 14A divalent linking group among -、-O-、-SO2- or -CO- is bonded to each other.

[0448] In the general formula (16), Y3 represents a single bond, -NR 14 - or -O-.

[0449] In the general formula (16), R 13 represents a group represented by the general formula (15).

[0450] Hereinafter, specific examples of the compound represented by the general formula (13) are shown. In addition, the present invention is not limited to these.

[0451]

Chemical formula 27

[0452]

[0453] Hereinafter, specific examples of the compound represented by the general formula (14) are shown. In addition, the present invention is not limited to these.

[0454]

Chemical formula 28

[0455]

[0456] When the compound represented by the general formula (13) and the compound represented by the general formula (14) are used in combination, the mass ratio of the compound represented by the general formula (13) to the compound represented by the general formula (14) is preferably 95:5 to 5:95, more preferably 95:5 to 50:50.

[0457] The production methods of the compound represented by the general formula (13) and the compound represented by the general formula (14) are not particularly limited, and known methods can be used. For example, the methods described in JP-A-2006-291194 and JP-A-2008-069343 can be cited.

[0458] [Mercaptan chain transfer agent (H)]

[0459] The red photosensitive composition of the present invention may contain a mercaptan chain transfer agent (H).

[0460] Examples of the mercaptan chain transfer agent (H) include monofunctional mercaptan compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, etc.;

[0461] Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, mercaptoacetic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutyric acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid;

[0462] Polyfunctional thiol compounds such as hexanethiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioacetate, ethylene glycol dithioacetate, ethylene glycol dithiopropionate, trimethylolpropane trimercaptoacetate, trimethylolpropane trimercaptopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetramercaptoacetate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0463] The thiol chain transfer agent (H) can be used alone or in combination of two or more.

[0464] The content of the thiol chain transfer agent (H) is preferably 0.5% by mass to 10% by mass in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0465] [Silane coupling agent (I)]

[0466] The red photosensitive composition of the present invention may contain a silane coupling agent (I).

[0467] The silane coupling agent (I) is a compound having a hydrolyzable group and a functional group other than the hydrolyzable group. The hydrolyzable group is a group that directly bonds to a silicon atom and generates a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among them, an alkoxy group is preferably used. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group.

[0468] Examples of the functional groups other than the above functional groups include an epoxy group, an amino group, a vinyl group, a (meth)acryloyl group, an isocyanate group, an isocyanurate group, a mercapto group, an oxetane group, a styryl group, and a urea group.

[0469] In addition, in this specification, the silane coupling agent (I) is not included in the resin (B) having an acidic group and the polymerizable compound (C).

[0470] Examples of the silane coupling agent (I) include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, The hydrochloride of silane, vinyl trimethoxysilane, vinyl triethoxysilane, 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, 3-acryloxypropyl trimethoxysilane, 3-isocyanate propyl triethoxysilane, tris-(trimethoxysilylpropyl) isocyanurate, 3-mercaptopropyl methyl dimethoxysilane, 3-mercaptopropyl trimethoxysilane, p-phenylene trimethoxysilane, 3-ureidopropyl trialkoxysilane, etc.

[0471] Examples of commercially available products of the silane coupling agent (I) include KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-9103P, and KBM-1003P manufactured by Shin-Etsu Silicone Co., Ltd. -1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KB E-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-50, etc.

[0472] The silane coupling agent (I) may be a polymer type. Examples of the polymer type include polysiloxane type and organic polymer type.

[0473] The polysiloxane type is a compound in which the hydrolyzable group and the functional groups other than the above are bonded to a polymer having a polysiloxane skeleton in the main chain. Examples of commercially available polysiloxane type compounds include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicone Co., Ltd.

[0474] The organic polymer type is a silane coupling agent (I) in which the hydrolyzable group and other functional groups are bonded in an organic polymer having an organic structure in the main chain. Commercially available products of the organic polymer type include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0475] The silane coupling agent (I) preferably contains a compound represented by the following general formula (17). Since the compound represented by the general formula (17) has a urethane bond, it forms hydrogen bonds with the urethane bond and the functional groups of other components contained in the photosensitive composition, resulting in a firm film. In addition, since the urethane bond has flexibility, it is presumed to form a firm and flexible film.

[0476]

Chemical formula 29

[0477] General formula (17)

[0478]

[0479] In the general formula (17), three R1s each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 1 to 8 carbon atoms, Q is a group represented by any one of the following general formulas (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0480]

Chemical formula 30

[0481]

[0482] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulas (Q-1) to (Q-4), R4s each independently represent a hydrogen atom or a methyl group. * is a bonding bond to an oxygen atom.

[0483] In the general formula (17), three R1s are preferably methyl groups.

[0484] In the general formula (17), Q is preferably the general formulas (Q-1) to (Q-3).

[0485] The molecular weight (formula weight) or weight average molecular weight of the silane coupling agent (I) is preferably 100 to 3,000, more preferably 150 to 1,500.

[0486] The acid value of the silane coupling agent (I) is preferably 10 mgKOH / g or less.

[0487] The silane coupling agent (I) can be used alone or in combination of two or more.

[0488] The content of the silane coupling agent (I) is preferably 0.1% by mass to 10% by mass in 100% by mass of the nonvolatile component of the red photosensitive composition.

[0489] [Leveling agent (J)]

[0490] The red photosensitive composition of the present invention may contain a leveling agent (J), thereby improving wettability and drying properties on a substrate during coating.

[0491] Examples of the leveling agent (J) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0492] Examples of the silicon-based surfactant include linear polymers composed of siloxane bonds, modified siloxane polymers having an organic group introduced into a side chain or a terminal, and polymers having a siloxane structure in a side chain.

[0493] Examples of commercially available products include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570, and FZ-7002 and 211 made by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc. manufactured by Shin-Etsu Silicone Co., Ltd.

[0494] In addition, polymers described in International Publication No. 2019 / 078080, International Publication No. 2021 / 131726, International Publication No. 2022 / 050062, International Publication No. 2022 / 059492, International Publication No. 2022 / 130990, and International Publication No. 2022 / 244586 can be cited.

[0495] Examples of the fluorine-based surfactant include surfactants and leveling agents having a fluorocarbon chain.

[0496] Examples of commercially available products include SURFLON S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., MEGAFAC F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Co., Ltd., EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and FTERGENT 602A manufactured by NEOS Corporation.

[0497] Examples of commercially available nonionic surfactants include EMULGEN 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMUL PD-420, PD-430, PD-430S, PD-450, and RHEODOL manufactured by Kao Corporation. SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, SUPER SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, SUPER TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, EMANON1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), AMIET102, 105, 105A, 302, 320, AMINON PK-02S, L-02, HOMOGENOL L-95, ADEKA PLURONIC (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA, (meth)acrylic acid copolymer POLYFLOW No.75, No.90, No.95 manufactured by Kyoeisha Chemical Co., Ltd., etc.

[0498] Examples of commercially available cationic surfactants include ACETAMIN 24, QUARTAMIN 24P, 60W, and 86P CONC manufactured by Kao Corporation.

[0499] Examples of commercially available anionic surfactants include FTERGENT 100 and 150 manufactured by NEOS, and ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, and EC-8600 manufactured by ADEKA.

[0500] Examples of commercially available amphoteric surfactants include AMPHITOL 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0501] The leveling agent (J) can be used alone or in combination of two or more.

[0502] It is preferable that content of the leveling agent (J) is 0.001 mass % - 2.0 mass % in 100 mass % of the nonvolatile components of the red photosensitive composition.

[0503] [Organic solvent (K)]

[0504] The red photosensitive composition of the present invention may contain an organic solvent (K).

[0505] Examples of the organic solvent (K) include 1,2,3-trichloropropane, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butanediol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-dimethylbenzene, and m-xylene. Ethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, 1-butanol, 2-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotert-butyl Ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

[0506] From the viewpoint of storage stability, the organic solvent (K) preferably contains an organic solvent having a hydroxyl group. Specifically, dipropylene glycol monobutyl ether, diethylene glycol hexyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, diacetone alcohol, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, ethylene glycol monobutyl ether, 3-methyl-1-butanol, ethyl lactate, diethylene glycol monomethyl ether, cyclohexanol, 3-methoxy-1-butanol, benzyl alcohol, 2-methyl-1-butanol, ethylene glycol monoethyl ether, 2-butanol, furfuryl alcohol, 1-butanol, ethylene glycol monomethyl ether, ethanol, tripropylene glycol monobutyl ether, 3-methoxy-3-methyl-1-butanol, 1,3-butanediol, 1,3-butylene glycol, 2-methyl-1,3-propanediol, etc. can be mentioned.

[0507] From the viewpoint of storage stability, the content of the organic solvent having a hydroxyl group is preferably 0.1% by mass to 20% by mass in 100% by mass of the organic solvent (K).

[0508] The organic solvent (K) can be used alone or in combination of two or more.

[0509] The content of the organic solvent (K) is preferably such an amount that the nonvolatile component of the red photosensitive composition is 5% by mass to 60% by mass.

[0510] [Other ingredients (L)]

[0511] The red photosensitive composition of the present invention may contain other components (L) in addition to the above components. Examples of other components (L) include resins without acidic groups (e.g., resins with basic groups, etc.), pigment derivatives without basic groups (e.g., pigment derivatives with acidic groups, etc.), polymerization inhibitors, antioxidants, sensitizers, acid generators, alkali generators, curing accelerators, curing catalysts, near infrared absorbers, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, insulating materials, etc.

[0512] [Content of specific metal elements]

[0513] In the red photosensitive composition of the present invention, the total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) contained in the red photosensitive composition is preferably 500 mass ppm or less.

[0514] The red photosensitive composition having the total amount of the specific metal element within the above range has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal element can be measured by inductively coupled plasma emission spectrometry (ICP).

[0515] [Water content]

[0516] In the red photosensitive composition of the present invention, the content of water contained in the red photosensitive composition is preferably 2.0% by mass or less.

[0517] The red photosensitive composition having a water content within the above range has excellent dispersion stability and sensitivity even after storage for a period of time. The water content can be measured by a known method such as the Karl Fischer method.

[0518] [Method for producing red photosensitive composition]

[0519] The red photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing, the components can be mixed together or mixed in sequence after dissolving and dispersing the components in the polymerizable compound (C) and the organic solvent (K).

[0520] For example, a dispersion can be prepared by adding a color material (A), a resin having an acidic group (B), and an organic solvent (K) and performing a dispersion treatment. Then, the dispersion can be prepared by blending and mixing a polymerizable compound (C), a polymerization initiator (D), and the like. In addition, the timing of blending each material is arbitrary. In addition, multiple dispersion steps can also be performed.

[0521] Examples of the disperser for performing the dispersion treatment include a double roll mill, a triple roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, a ring-shaped bead mill, and an attritor.

[0522] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably 30 nm to 200 nm, more preferably 40 nm to 200 nm. When the particles have an appropriate particle size, a red photosensitive composition having high dispersion stability can be easily obtained.

[0523] The determination method of average dispersed particle diameter (secondary particle diameter) is for example using the micro track (Micro track) UPA-EX150 of Nikkiso Co., Ltd. adopting dynamic light scattering method (FFT power spectrum method), particle permeability is set to absorption mode, particle shape is set to non-spherical, and D50 particle diameter is set to average diameter. The diluting solvent used for determination uses the organic solvent used in dispersion respectively for the sample treated with ultrasound, if measured immediately after sample adjustment, then it is easy to obtain the result with few deviations, so it is preferred.

[0524] The red photosensitive composition is preferably subjected to centrifugal separation, filtration using a sintered filter, a membrane filter, or the like to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and mixed dust. The red photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0525] The red photosensitive composition of the present invention is preferably used for pattern formation in photolithography. However, the present invention is not limited thereto.

[0526] <Film>

[0527] The film of the present invention is a film formed of the above-mentioned red photosensitive composition. The film is preferably a patterned film, but may be used as a flat film without forming a pattern.

[0528] [Method for producing film]

[0529] In terms of film production, from the perspective of the environment, the heating temperature in the entire process is preferably 150° C. or less, and more preferably 130° C. or less. In addition, by heating at a temperature below 150° C., these properties can be maintained when an organic EL element is used as a light source for an image display device, when the photoelectric conversion film of an image sensor is an organic material, and when a substrate that is weak to heat such as a plastic film is used. In addition, the heating temperature is preferably 50° C. or more.

[0530] In the preparation of the film, first, a red photosensitive composition is coated on a substrate. Examples of the substrate include glass, resin, silicon and the like. The glass is preferably colorless and transparent. In addition, colored glass such as blue glass can be used depending on the application. The substrate may have an organic light-emitting layer. In addition, the substrate may use an imaging element such as a CCD or CMOS. In addition, a primer layer for improving the close contact between the upper portion and the layer, preventing the diffusion of substances, and flattening the surface may be provided on the substrate as required.

[0531] The coating method may be a known method, for example, a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a cast coating method, an inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. may be used.

[0532] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 μm to 20.0 μm, more preferably 0.3 μm to 10.0 μm.

[0533] Next, a pattern is formed. The method for forming a pattern can include photolithography and dry etching. Among them, photolithography is preferred. In addition, when used as a flat film, the process of forming a pattern may not be performed, and after coating, the entire surface may be dried and exposed as needed.

[0534] Hereinafter, a method of forming a pattern by photolithography will be described in detail.

[0535] The photolithography method is to apply the red photosensitive composition of the present invention on a substrate to form a layer, dry it at a temperature of 150° C. or less as needed, expose it to light in a pattern through a mask (exposure step), remove the unexposed part by alkaline development (development step), and then heat the pattern (heating step).

[0536] [Exposure process]

[0537] The exposure process is to expose a specific pattern to the layer formed by coating through a mask using an exposure device such as a stepper. In this way, the exposed portion can be cured. Active energy rays used for exposure include, for example, ultraviolet rays such as g-line (wavelength 436nm), h-line (wavelength 405nm), and i-line (wavelength 365nm). In addition, light with a wavelength of 300nm or less can also be used. Light with a wavelength of 300nm or less includes, for example, KrF line (wavelength 248nm), ArF line (wavelength 193nm), etc.

[0538] In addition, during exposure, light may be irradiated continuously or repeatedly irradiated and stopped in a short time (for example, milliseconds or less) cycle to perform exposure (pulse exposure).

[0539] Alternatively, a plurality of active energy rays may be used in combination, or the exposure may be performed in a plurality of times.

[0540] 〔Development process〕

[0541] Next, by treating with an alkaline developer, the unexposed portion of the layer is dissolved into the alkaline developer, and only the cured portion remains, thereby obtaining a patterned film.

[0542] Examples of the alkaline developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.

[0543] The concentration of the alkaline developer is preferably 0.001% to 10% by mass, more preferably 0.01% to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When an appropriate pH is used, roughness and peeling of the pattern are suppressed, and the residual film rate after development is increased.

[0544] Examples of the developing method include a dipping method, a spray method, and a paddle method. The developing temperature is preferably 15° C. to 40° C. After the alkaline development, washing with pure water is preferably performed.

[0545] 〔Heating process〕

[0546] After development, heat treatment is performed to improve the durability of the film.

[0547] The heating temperature is preferably 150° C. or lower, more preferably 130° C. or lower. The heating time is preferably about 2 minutes to 2 hours.

[0548] <Color filter>

[0549] The color filter of the present invention has the above-mentioned film. The color filter of the present invention can be produced by the same method as that for the above-mentioned film.

[0550] <Solid-state imaging device>

[0551] A solid-state imaging device according to the present invention includes the above-mentioned color filter.

[0552] The solid-state imaging element includes the color filter of the present invention and is not particularly limited as long as it functions as a solid-state imaging element. For example, the following configurations can be mentioned.

[0553] The structure is as follows: on a substrate, there are a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transmission electrode composed of polysilicon, etc., a light-shielding film having an opening only for the light-receiving portion of the photodiode is provided on the photodiode and the transmission electrode, a device protection film composed of silicon nitride, etc. formed in a manner covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film, and a color filter of the present invention is provided on the device protection film. Furthermore, it is also possible to have a structure having a focusing mechanism (for example, a microlens, etc., the same below) on the device protection film and below the color filter (on the side close to the substrate), a structure having a focusing mechanism on the optical filter, etc. In addition, the filter may also have a structure in which a solidified film forming each color pixel is buried in a space divided into, for example, a grid shape by a partition wall. At this time, the partition wall is preferably of a low refractive index relative to each color pixel.

[0554] The imaging device including the solid-state imaging element of the present invention can be used in various applications such as digital cameras, electronic devices having an imaging function (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0555] <Image display device>

[0556] The image display device of the present invention includes the above-mentioned color filter. Examples of the image display device include a liquid crystal display and an organic EL display.

[0557] The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the following liquid crystal display configuration can be cited.

[0558] The liquid crystal display comprises a color filter, an opposing substrate having a TFT array substrate, and a liquid crystal layer formed between the color filter and the opposing substrate. As the driving mode of the liquid crystal display, for example, a TN mode, an IPS mode, an OCB mode, and an MVA mode can be cited. The opposing substrate can be appropriately selected for use according to the driving mode. The liquid crystal layer can use various liquid crystals with different dielectric anisotropies and these mixtures according to the driving mode.

[0559] [Example]

[0560] The present invention is described in more detail below by way of examples. However, the present invention is not limited to the examples. In addition, "parts" means "parts by mass" and "%" means "% by mass". In addition, in the present invention, the non-volatile component or non-volatile component concentration refers to the residual component by mass after standing in an oven at 110°C for 3 hours.

[0561] Prior to the examples, each measurement method is described.

[0562] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and absorption coefficient (L / mol·cm) of the resin were measured as follows.

[0563] (Molecular weight)

[0564] The number average molecular weight (Mn) and weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) is used as an apparatus, two separation columns are connected in series, and two "TSK-GEL SUPER HZM-N" are connected in the fillers of the two columns. The oven temperature is 40°C, and tetrahydrofuran (THF) solution is used as the eluent, and the measurement is performed at a flow rate of 0.35 mL / min. The sample is dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters are injected. The molecular weight is a polystyrene conversion value.

[0565] (Acid value)

[0566] 80 ml of acetone and 10 ml of water were added to 0.5 g to 1 g of the sample solution and stirred to make it uniformly dissolved. A 0.1 mol / L KOH aqueous solution was used as a titrant and titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g). Next, the acid value per unit non-volatile component was calculated based on the acid value of the solution and the non-volatile component concentration of the solution.

[0567] (Absorption coefficient)

[0568] 0.001 g of the polymerization initiator was dissolved in 0.01 L of propylene glycol monomethyl ether acetate to prepare a 0.1 mass % measurement solution. Further, the obtained 0.1 mass % measurement solution was diluted with propylene glycol monomethyl ether acetate to prepare 0.01 mass % and 0.001 mass % measurement solutions. Using a spectrophotometer ("U-3010" manufactured by Hitachi High-Technologies Corporation), the absorbance of the measurement solution of each concentration at a wavelength of 365 nm was measured, and the absorption coefficient (L / mol·cm) was calculated based on the slope when the horizontal axis was the molar concentration and the vertical axis was the absorbance.

[0569] <Manufacturing of color material (A)>

[0570] (Purple color material (A4-1))

[0571] 67.3 parts of methyl ethyl ketone were added to a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75°C under a nitrogen stream. 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 uniformly mixed and added to a dropping funnel, which was attached to a four-necked separable flask and added dropwise for 2 hours. Two hours after the addition was completed, the polymerization yield was confirmed to be 98% or more based on the non-volatile components and the weight average molecular weight was 6,830, and the mixture was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added thereto, and the mixture was reacted at 50°C for 2 hours, and then the mixture was heated to 80°C for 1 hour and reacted for 2 hours to obtain Resin 1.

[0572] Next, 30 parts of resin 1 in terms of non-volatile components were added to 2,000 parts of water, and the mixture was stirred and mixed thoroughly, and then heated to 60°C. On the other hand, an aqueous solution of 10 parts of CI Acid Red 52, a compound having a xanthene skeleton, was dissolved in 90 parts of water, and the solution was added dropwise to the resin 1 solution just now in small amounts. After the addition, the mixture was stirred at 60°C for 120 minutes to allow the reaction to proceed sufficiently. As a confirmation of the end point of the reaction, the reaction solution was added dropwise to filter paper, and the end point was determined to be the time when the oozing disappeared, and the salt compound was determined to be obtained. After cooling to room temperature while stirring, the mixture was filtered by suction, and after washing with water, the salt compound remaining on the filter paper was dried by removing moisture with a dryer to obtain a purple color material (A4-1) of a salt compound of CI Acid Red 52, a compound having a xanthene skeleton, and resin 1. At this time, the content of the component derived from CI Acid Red 52 in the purple color material (A4-1) was 25% by mass.

[0573] (Purple color material (A4-2))

[0574] A violet color material (A4-2) was produced in the same manner as the violet color material (A4-1) except that CI Acid Red 52 was replaced with CI Acid Red 289. At this time, the content of the component derived from CI Acid Red 289 in the violet color material (A4-2) was 25% by mass.

[0575] (Purple color material (A4-3))

[0576] Into a reaction device equipped with a gas introduction pipe, a capacitor, a stirring blade and a thermometer, 18.2 parts of methyl methacrylate, 14.8 parts of n-butyl methacrylate, 14.8 parts of 2-ethylhexyl methacrylate, 10.0 parts of methacrylic acid, 15.0 parts of 3-ethyl-3-methacryloyloxymethyloxetane and 15.0 parts of tert-butyl methacrylate were added, and nitrogen was circulated while stirring at 50°C for 1 hour to replace the system with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride and 62.3 parts of propylene glycol monomethyl ether were added, and the temperature was raised to 100°C under a nitrogen flow to start the polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile component was measured. The polymerization conversion rate was confirmed to be 98% or more by conversion based on the non-volatile component. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methyl chloride of methacrylate as the second block monomer were added to the reaction apparatus, and the reaction was continued by stirring while maintaining the temperature at 100° C. in a nitrogen atmosphere. Two hours after the addition of dimethylaminoethyl methyl chloride of methacrylate, the polymerization solution was sampled and the nonvolatile component was measured. The polymerization conversion rate of the second block was confirmed to be 98% or more by conversion based on the nonvolatile component. After cooling to 50° C., methanol was added to obtain resin 2. The weight average molecular weight was 7,700.

[0577] Next, 30 parts of resin 2 calculated as non-volatile components are added to 2,000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60°C. On the other hand, an aqueous solution of 10 parts of a compound represented by the following chemical formula (18) dissolved in 90 parts of water is prepared and added dropwise to the resin 2 solution just now in small amounts. After the addition, the mixture is stirred at 60°C for 120 minutes to allow the reaction to proceed sufficiently. As confirmation of the end point of the reaction, the reaction solution is added dropwise to filter paper, and the end point is determined when the oozing disappears, and the salt compound is determined to be obtained. After cooling to room temperature while stirring, suction filtration is performed, and after washing with water, the salt compound remaining on the filter paper is dried by removing moisture with a dryer to obtain 32 parts of a purple color material (A4-3) of the compound represented by the chemical formula (18) and the salt compound of resin 2. At this time, the content of the component derived from the compound represented by the chemical formula (18) in the purple color material (A4-3) is 25% by mass.

[0578] Chemical formula (18)

[0579]

Chemistry 31

[0580]

[0581] (Purple color material (A4-4))

[0582] The following purple color material (A4-4) was synthesized according to paragraphs 0102 to 0104 of Japanese Patent Application Laid-Open No. 2015-57487. The numerical values ​​indicated in the repeating unit are mass ratios.

[0583]

Chemistry 32

[0584]

[0585] <Production of Resin (B) Having an Acidic Group>

[0586] (Solution of Resin (B1-1) Having Aromatic Carboxyl Groups)

[0587] In a reaction vessel equipped with a gas introduction tube, a thermometer, a capacitor, 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 added, and after nitrogen substitution, the reaction was carried out at 120°C for 5 hours (first step). The acid value was measured to confirm that 95% or more of the anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methacrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) were added in terms of non-volatile components, 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). The reaction was confirmed to have occurred at 95% by nonvolatile content measurement. 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 added and the reaction was continued until IR confirmed that the isocyanate group-based 2,270 cm -1 The peak disappears (third step). After cooling, PGMAc is added to make the non-volatile component reach 30% by mass, and a resin (B1-1) solution with an aromatic carboxyl group is prepared. Pyromellitic anhydride / 3-mercapto-1,2-propylene glycol = 0.8 (molar ratio), the acid value is 68 mgKOH / g, and the weight average molecular weight is 13,000.

[0588] (Solution of resin (B1-2) having aromatic carboxyl groups)

[0589] Add 20.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, 5.0 parts of methac, and 25.0 parts of PGMAc to a reaction container equipped with a gas introduction tube, a thermometer, a capacitor, and a stirrer, and replace with nitrogen. Heat the reaction container to 50°C, and add 6.0 parts of 3-mercapto-1,2-propanediol. Raise the temperature to 90°C, add a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.7 parts of PGMAc, and react for 10 hours. Confirm that 95% of the reaction has occurred by measuring the non-volatile content.

[0590] Next, 14.5 parts of pyromellitic anhydride, 38.0 parts of PGMAc, 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. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The half-esterification of the anhydride was confirmed by measuring the acid value, and the reaction was terminated. After cooling, PGMAc was added to make the non-volatile component reach 30% by mass, and a resin (B1-2) solution having an aromatic carboxyl group was prepared. Pyromellitic anhydride / 3-mercapto-1,2-propylene glycol = 1.2 (molar ratio), the acid value is 105 mgKOH / g, and the weight average molecular weight is 9,500.

[0591] (Solution of resin (B1-3) having aromatic carboxyl groups)

[0592] In a reaction vessel equipped with a gas introduction pipe, a temperature, a capacitor, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were added, and nitrogen replacement was performed. The reaction vessel was heated and stirred to 50°C, 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 added to 90 parts of PGMAc was added, and the reaction was carried out for 10 hours. The non-volatile component measurement confirmed that 95% of the reaction occurred. 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 acid value measurement confirmed that 98% or more of the anhydride was half-esterified, and the reaction was terminated. After cooling, PGMAc was added to make the nonvolatile content 30% by mass to prepare a resin (B1-3) solution having an aromatic carboxyl group. Pyromellitic dianhydride / 3-mercapto-1,2-propanediol = 0.78 (molar ratio), acid value 70 mgKOH / g, weight average molecular weight 8,500.

[0593] (Solution of resin (B2-1) having no aromatic carboxyl group)

[0594] According to International Publication No. 2016 / 103994, a solution of the following copolymer (resin (B2-1) without an aromatic carboxyl group) with a non-volatile component of 30% by mass is prepared by adding PGMAc. The acid value is 51.7 mgKOH / g, and the weight-average molecular weight is 13,000. The values noted in the repeating units of the main chain are molar ratios, and the values noted in the repeating units of the side chain are the number of repetitions of the repeating site.

[0595]

Chemical formula 33

[0596]

[0597] (Solution of resin (B2-2) without an aromatic carboxyl group)

[0598] According to International Publication No. 2016 / 103994, a solution of the following copolymer (resin (B2-2) without an aromatic carboxyl group) with a non-volatile component of 30% by mass is prepared by adding PGMAc. The acid value is 58.2 mgKOH / g, and the weight-average molecular weight is 10,000. The values noted in the repeating units of the main chain are molar ratios, and the values noted in the repeating units of the side chain are the number of repetitions of the repeating site.

[0599]

Chemical formula 34

[0600]

[0601] (Solution of resin (B2-3) without an aromatic carboxyl group)

[0602] Into a flask equipped with a stirring device, a dropping funnel, a capacitor, a thermometer, and a gas inlet tube, 100 parts of propylene glycol monomethyl ether was added, and while stirring, nitrogen replacement was carried out and the temperature was raised to 78 °C. Then, a mixture of 25.2 parts of KARENZ MOI-DEM (diethyl 2-[[[[(2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]malonate manufactured by Showa Denko K.K.), 31.2 parts of 2-hydroxyethyl methacrylate, 37.5 parts of dicyclopentanyl methacrylate, 20.7 parts of methacrylic acid, and 27.0 parts of methyl methacrylate and a solution prepared by adding 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) to 50 parts of PGMAc and dissolving were respectively dropped from the dropping funnel into the flask. After the dropping was completed, the reaction was carried out by stirring at 78 °C for 3 hours.

[0603] Then, PGMAc was added to adjust the non-volatile component to 30% by mass, and a solution of resin (B2-3) without an aromatic carboxyl group was adjusted. The acid value is 74 mgKOH / g, and the weight-average molecular weight is 8,000.

[0604] (Solution of resin (B2-4) not having an aromatic carboxyl group)

[0605] 190.2 parts of diethyl malate, 0.17 parts of 2,6-di-tert-butyl-4-methylphenol, and 0.33 parts of dibutyltin dilaurate were added to a four-necked flask equipped with a stirring device, a thermometer, a dropping funnel, and a reflux cooler, and stirred, and cooled to 15°C to 20°C. Then, 141.1 parts of 2-acryloyloxyethyl isocyanate were added dropwise from the dropping funnel while maintaining the temperature at 15°C to 20°C and stirring. After the addition was completed, the mixture was stirred at 25°C for 13 hours to react, thereby obtaining compound a.

[0606] Next, 150 parts of propylene glycol monomethyl ether were added to a flask equipped with a stirring device, a dropping funnel, a capacitor, a thermometer, and a gas introduction tube, and the temperature was raised to 78°C while stirring while replacing with nitrogen. 148.8 parts of compound a, 24.7 parts of KARENZMOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko K.K.), 25.5 parts of 2-hydroxyethyl methacrylate, 8.6 parts of 2-ethylhexyl acrylate, and 17.4 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and dropped from the dropping funnel into the flask. After the dropwise addition was completed, the mixture was stirred at 78°C for 3 hours to react, and then 0.2 parts of 1,8-diazabicyclo[5.4.0]-undecene-7 was added, and the mixture was further stirred at 78°C for 30 minutes.

[0607] Next, 9.9 parts of succinic anhydride and 0.5 parts of lithium naphthenate (catalyst) were added, and the mixture was stirred at 78°C for 1 hour.

[0608] Then, PGMAc was added so that the nonvolatile content was 30% by mass to prepare a resin (B2-4) solution having no aromatic carboxyl group. The acid value was 44 mgKOH / g and the weight average molecular weight was 12,500.

[0609] (Solution of resin (B2-5) having no aromatic carboxyl group)

[0610] After adding 100 parts of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a capacitor, a thermometer, and a gas introduction tube, the temperature was raised to 90°C while stirring while replacing with nitrogen. Next, a mixture of 20.7 parts of ethyl 2-(acetoacetoxy)methacrylate, 26.7 parts of methacrylic acid, and 52.6 parts of dicyclopentyl methacrylate and a solution in which 5.0 parts of 2,2'-azobis(isobutyric acid)dimethyl ester was added to 30 parts of PGMAc and dissolved were added dropwise from the dropping funnel to the flask. After the addition was completed, the mixture was stirred at 90°C for 6 hours to react.

[0611] Then, the mixture was cooled to 40° C., 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexyl methacrylate, and 4.7 parts of triphenylphosphine were added, and the mixture was heated to 110° C. and stirred for 10 hours to allow the mixture to react.

[0612] Then, PGMAc was added so that the nonvolatile content was 30% by mass to prepare a resin (B2-5) solution having no aromatic carboxyl group. The acid value was 103 mgKOH / g and the weight average molecular weight was 14,300.

[0613] (Solution of resin (B2-6) not having an aromatic carboxyl group)

[0614] After adding 200 parts of 3-methoxy-1-butanol to a flask equipped with a stirring device, a dropping funnel, a capacitor, a thermometer, and a gas introduction tube, the temperature was raised to 105°C while stirring while replacing with nitrogen. Next, a mixture of 106.9 parts of 3-methacryloxypropyltrimethoxysilane, 40.8 parts of methacrylic acid, and 125 parts of methyl methacrylate and a solution containing 27.3 parts of 2,2'-azobis(isobutyric acid)dimethyl ester were dropped from the dropping funnel into the flask. After the dropwise addition was completed, the mixture was reacted for 2 hours while stirring at 105°C.

[0615] Then, PGMAc was added so that the nonvolatile content was 30% by mass to prepare a resin (B2-6) solution having no aromatic carboxyl group. The acid value was 99 mgKOH / g and the weight average molecular weight was 7,100.

[0616] (Solution of resin (B2-7) not having an aromatic carboxyl group)

[0617] After adding 100 parts of propylene glycol monomethyl ether to a flask equipped with a stirring device, a dropping funnel, a capacitor, a thermometer, and a gas introduction tube, the temperature was raised to 90°C while stirring while replacing with nitrogen. Next, a mixture of 35 parts of tert-butyl methacrylate, 5 parts of 2-(acetoacetoxy)ethyl methacrylate, 10 parts of N-benzylmaleimide, 20 parts of 2-hydroxyethyl methacrylate, 17.1 parts of methacrylic acid, and 2 parts of tert-butylperoxy-2-ethylhexanoate (polymerization initiator) and a solution of 0.6 parts of n-dodecyl mercaptan mixed with 20 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition was completed, the temperature was kept at 90°C for 30 minutes, then raised to 115°C, and stirred for 90 minutes to react.

[0618] Then, PGMAc was added so that the nonvolatile content was 30% by mass to prepare a resin (B2-7) solution having no aromatic carboxyl group. The acid value was 98 mgKOH / g and the weight average molecular weight was 19,500.

[0619] (Solution of resin (B2-8) not having an aromatic carboxyl group)

[0620] 200 parts of propylene glycol monomethyl ether were added to a reaction container equipped with a thermometer, a cooling tube, a nitrogen inlet tube and a stirring device in a separable four-necked flask, and the container was heated to 120° C. while nitrogen was injected into the container. At the same temperature, a mixture of 56.86 parts of glycidyl methacrylate, 66.09 parts of dicyclopentanyl methacrylate and 31.25 parts of styrene and a solution in which 5.0 parts of azobisisobutyronitrile as a polymerization initiator was dissolved in PGMAc were dropped by a dropper over 2.5 hours to carry out a polymerization reaction.

[0621] After the dropwise addition, the mixture was stirred for further 2 hours at 120° C. to allow the mixture to react. Next, the air in the flask was replaced, and 28.82 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added and stirred for reaction at 120° C. for 5 hours.

[0622] Furthermore, 32.0 parts of succinic anhydride and 0.5 parts of triethylamine were added, and the mixture was stirred at 120° C. for 4 hours to allow the mixture to react.

[0623] Then, PGMAc was added so that the nonvolatile content was 30% by mass to prepare a resin (B2-8) solution having no aromatic carboxyl group. The resin had an acid value of 77 mgKOH / g and a weight average molecular weight of 10,000.

[0624] <Production of Compound (E2) Having Blocked Isocyanate Group>

[0625] (Production of Compound E2-2 Having Blocked Isocyanate Group)

[0626] Into a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, 100 parts by mass of hexamethylene diisocyanate (hereinafter referred to as HDI) was added under a nitrogen flow, the temperature in the reactor was maintained at 60°C while stirring, and 0.095 parts by mass of trimethylbenzylammonium hydroxide was added to react. After 4.5 hours, when the conversion rate reached 40% by mass, 0.02 parts by mass of phosphoric acid was added to stop the reaction. After filtering the reaction solution, a thin film evaporator was used to remove unreacted HDI to obtain an isocyanurate-type polyisocyanate (hereinafter referred to as "E2 precursor"). The NCO content of the obtained E2 precursor was 22.0% by mass, the number average molecular weight was 655, and the average number of isocyanate groups was 3.43. In addition, the obtained E2 precursor was subjected to 1 H-NMR analysis confirmed the presence of an isocyanurate group.

[0627] In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, the above-mentioned E2 precursor: 100 parts by mass, diethyl malonate (100 mol% relative to 100 mol% of NCO groups) were added under a nitrogen stream, and butyl acetate was further added to adjust the non-volatile component to 60% by mass. Then, while stirring, a methanol solution containing sodium methoxide (28% by mass relative to the total mass of the solution) was added dropwise: 1.0 parts by mass, and the external bath was adjusted so that the solution temperature reached 55°C, and the blocking reaction was carried out at 55°C for 5 hours to terminate the reaction. Thus, a compound E2-2 having a blocked isocyanate group and containing the above-mentioned (X-1) as a blocked isocyanate group and having a non-volatile component of 60% by mass was obtained.

[0628] (Production of Compound E2-3 Having Blocked Isocyanate Group)

[0629] In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, the above-mentioned E2 precursor: 100 parts by mass, diethyl malonate (70 mol% relative to 100 mol% of NCO groups) and dibutyl malonate (30 mol% relative to 100 mol% of NCO groups) were added under a nitrogen flow, and butyl acetate was further added to adjust the non-volatile content to 60% by mass. Then, while stirring, a methanol solution containing sodium methoxide (28% by mass relative to the total mass of the solution) was added dropwise: 1.0 parts by mass, and the external bath was adjusted so that the solution temperature reached 55°C, and the blocking reaction was carried out at 55°C for 5 hours to terminate the reaction. Thus, a compound E2-3 having a blocked isocyanate group containing the above-mentioned (X-1) and (X-8) as blocked isocyanate groups at a molar ratio of 70:30 was obtained.

[0630] (Production of Compound E2-4 Having Blocked Isocyanate Group)

[0631] In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, the above-mentioned E2 precursor: 100 parts by mass, diethyl malonate (30 mol% relative to 100 mol% of NCO groups) and dibutyl malonate (70 mol% relative to 100 mol% of NCO groups) were added under a nitrogen stream, and butyl acetate was further added to adjust the non-volatile content to 60% by mass. Then, while stirring, a methanol solution containing sodium methoxide (28% by mass relative to the total mass of the solution) was added dropwise: 1.0 parts by mass, and the external bath was adjusted so that the solution temperature reached 55°C, and the blocking reaction was carried out at 55°C for 5 hours to terminate the reaction. Thus, a compound E2-4 having a blocked isocyanate group containing the above-mentioned (X-1) and (X-8) as blocked isocyanate groups at a molar ratio of 30:70 and a non-volatile content of 60% by mass was obtained.

[0632] (Production of Compound E2-5 Having Blocked Isocyanate Group)

[0633] In a four-necked flask equipped with a thermometer, a stirring blade and a reflux cooling tube, 100 parts by mass of the E2 precursor, diisopropyl malonate (70 mol% relative to 100 mol% of the NCO group) and di-tert-butyl malonate (30 mol% relative to 100 mol% of the NCO group) were added under a nitrogen stream, and butyl acetate was further added to adjust the non-volatile content to 60% by mass. Then, while stirring, a methanol solution containing sodium methoxide (28% by mass relative to the total mass of the solution) was added dropwise: 1.0 parts by mass, and the external bath was adjusted so that the solution temperature reached 55°C, and the blocking reaction was carried out at 55°C for 5 hours to terminate the reaction. Thus, a compound E2-5 having a blocked isocyanate group containing the above-mentioned (X-4) and (X-7) as blocked isocyanate groups in a molar ratio of 70:30 was obtained.

[0634] <Manufacturing of dispersion>

[0635] (Dispersion 1)

[0636] The following raw materials were stirred and mixed to make them uniform, and then dispersed for 3 hours using zirconia beads with a diameter of 0.5 mm using an Eiger mill ("Mini Model M-250MKII" manufactured by EIGER JAPAN), and then filtered using a filter with a pore size of 1.0 μm to prepare dispersion 1. The nonvolatile content was 21.0 mass %.

[0637] Red color material (A1-1): 15.0 parts

[0638] Aromatic carboxyl resin (B1-1) solution: 15.0 parts

[0639] Pigment derivative with basic group (G-1): 1.5 parts

[0640] Organic solvent (K-1): 68.5 parts

[0641] (Dispersion 2-18)

[0642] Dispersions 2 to 18 were prepared in the same manner as in Dispersion 1 except that the raw materials and amounts described in Table 1-1 and Table 1-2 were changed.

[0643]

Table 1-1

[0644]

[0645]

Table 1-2

[0646]

[0647] The respective components described in Table 1-1 and Table 1-2 are as follows.

[0648] [Colorant (A)]

[0649] (Red colorant (A1))

[0650] A1-1: C.I. Pigment Red 264

[0651] A1-2: C.I. Pigment Red 179

[0652] A1-3: C.I. Pigment Red 177

[0653] (Yellow colorant (A2))

[0654] A2-1: C.I. Pigment Yellow 139

[0655] A2-2: C.I. Pigment Yellow 185

[0656] (Blue colorant (A3))

[0657] A3-1: C.I. Pigment Blue 15:6

[0658] The red colorant (A1), yellow colorant (A2), and blue colorant (A3) are each micronized by salt milling, thoroughly washed with ion-exchanged water to achieve the above-specified metal amount, and then used after drying.

[0659] [Pigment derivative (G)]

[0660] [Chemical formula 35]

[0661]

[0662] [Organic solvent (K)]

[0663] K-1: PGMAc

[0664] [Other components (L)]

[0665] L-1: LP-N21116 (manufactured by BYK Chemie GmbH, resin with basic groups, non-volatile content 30%)

[0666] L-2: Compound having the following structure (pigment derivative with acidic groups)

[0667] [Chemical formula 36]

[0668]

[0669] <Manufacture of red photosensitive composition>

[0670] [Example 1]

[0671] (Red photosensitive composition 1)

[0672] The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a red photosensitive composition 1. The nonvolatile component was 15.0% by mass. In Table 2-1, dispersions 1 and 8 were decomposed into constituent components and described, and the organic solvent (K-1) of the dispersion was included in the organic solvent (K).

[0673]

[0674]

[0675] [Examples 2 to 54 and Comparative Example 1]

[0676] (Red photosensitive compositions 2 to 55)

[0677] Red photosensitive compositions 2 to 55 were prepared in the same manner as in Example 1 using the raw materials and amounts described in Tables 2-1 to 2 to 6. In Tables 2-1 to 2 to 6, dispersions 1 to 18 are described by breaking down the components, and the organic solvent (K-1) of the dispersion is described as being contained in the organic solvent (K).

[0678]

Table 2-1

[0679]

[0680]

Table 2-2

[0681]

[0682]

Table 2-3

[0683]

[0684]

Table 2-4

[0685]

[0686]

Table 2-5

[0687]

[0688]

Table 2-6

[0689]

[0690] The raw materials described in Table 2-1 to Table 2-6 are as follows.

[0691] [Polymerizable compound (C)]

[0692] (Polymerizable compound (C1) having an amine structure)

[0693] C1-1: CN9906 (manufactured by Arkema, multifunctional acrylate having an amine structure)

[0694] C1-2: ARONIX MT-3041 (manufactured by Toagosei Co., Ltd., multifunctional acrylate having an amine structure)

[0695] (Polymerizable compound (C2) having a hydroxyl group)

[0696] C2-1: ARONIX M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)

[0697] C2-2: ARONIX M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[0698] (Polymerizable compound (C3) having a dendritic structure or a hyperbranched structure)

[0699] C3-1: Miramer SP-1106 (manufactured by Miwon Specialty Chemical Co., Ltd., a compound having a dendritic structure with an average number of 18 acryloyl groups)

[0700] C3-2: SIRIUS-501 (manufactured by Osaka Organic Chemical Industry Co., Ltd., a compound having a dendritic structure with an average number of 18 acryloyl groups, and a non-volatile content of 50% by mass)

[0701] (Other polymerizable compounds (C7))

[0702] C7-1: KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol EO-modified hexaacrylate)

[0703] [Polymerization initiator (D)]

[0704] (Polymerization initiator (D1))

[0705] D1-3: the above compound (D1-3) (absorption coefficient of light at a wavelength of 365 nm is 13,410 L / mol·cm)

[0706] D1-4: the above compound (D1-4) (absorption coefficient of light at a wavelength of 365 nm is 14,214 L / mol·cm)

[0707] D1-5: the above compound (D1-5) (absorption coefficient of light at a wavelength of 365 nm is 18,767 L / mol·cm)

[0708] D1-6: the above-mentioned compound (D1-6) (absorption coefficient of light at a wavelength of 365 nm: 7,051 L / mol·cm)

[0709] (Polymerization initiator (D2))

[0710] D2-1: the above compound (D2-1) (absorption coefficient of light at a wavelength of 365 nm is 18,334 L / mol·cm)

[0711] D2-2: the above compound (D2-2) (absorption coefficient of light at a wavelength of 365 nm: 8,845 L / mol·cm)

[0712] (Polymerization initiator (D3) other than polymerization initiator (D1))

[0713] D3-1: Irgacure OXE-02 (manufactured by BASF JAPAN, with an absorption coefficient of 2,401 L / mol·cm at a wavelength of 365 nm)

[0714] [Thermal crosslinking compound (E)]

[0715] (Compound (E1) having an epoxy group)

[0716] E1-1: EHPE-3150 (manufactured by DAICEL, a compound represented by the general formula (12), having an average of 15 epoxy groups and an epoxy equivalent of 170 g / eq to 190 g / eq)

[0717] (Compound having a blocked isocyanate group (E2))

[0718] E2-1: DURANATE MF-K60B (manufactured by Asahi Kasei Corporation, a compound blocked with an active methylene compound, non-volatile content 60% by mass)

[0719] E2-2: the above compound (E2-2) (a compound blocked with the above (X-1), non-volatile content 60% by mass)

[0720] E2-3: the above compound (E2-3) (a compound blocked with the above (X-1) and (X-8) at a molar ratio of 70:30, non-volatile content 60% by mass)

[0721] E2-4: the above compound (E2-4) (a compound blocked with the above (X-1) and (X-8) at a molar ratio of 30:70, non-volatile content 60% by mass)

[0722] E2-5: The above-mentioned compound (E2-5) (a compound of the above-mentioned (X-4) and (X-7) blocks in a molar ratio of 70:30, non-volatile content 60% by mass)

[0723] E2-6: Dilute BI7982 (manufactured by Baxenden Chemical Co., a compound blocked with a pyrazole compound, non-volatile content 70% by mass) with PGMAc to obtain a non-volatile content of 60%.

[0724] E2-7: Dilute BI7984 (manufactured by Baxenden Chemical Co., a compound blocked with an oxime compound, non-volatile content 75% by mass) with PGMAc to obtain a non-volatile content of 60%.

[0725] [Ultraviolet absorber (F)]

[0726] F-1: A mixture of 4,4'-bis(diethylamino)benzophenone and 2,2',4,4'-tetrahydroxydibenzophenone in a mass ratio of 5:5

[0727] F-2: A compound having the following structure

[0728]

Chemical formula 37

[0729]

[0730] [Mercaptan chain transfer agent (H)]

[0731] A mixture of mercapto succinic acid and pentaerythritol tetra(3-mercaptopropionate) in a mass ratio of 5:5

[0732] [Silane coupling agent (I)]

[0733] X-12-1048 (manufactured by Shin-Etsu Silicone Co., a compound represented by the general formula (17))

[0734] [Leveling agent (J)]

[0735] A mixture of BYK-330 (manufactured by BYK-Chemie GmbH, polyether-modified dimethylsiloxane) and a block copolymer having the following structure (n:m = 50:50 (mol%)) in a mass ratio of 8:2

[0736]

Chemical formula 38

[0737]

[0738] [Organic solvent (K)]

[0739] K-1: PGMAc

[0740] K-2: Cyclohexanone

[0741] K-3: 3-ethoxypropionic acid ethyl ester

[0742] As described above, K-1, K-2 and K-3 were mixed at a mass ratio of 8:1:1 to obtain an organic solvent (K).

[0743] <Evaluation of red photosensitive composition>

[0744] The following evaluations were performed on the obtained red photosensitive compositions. The evaluation results are shown in Tables 3-1 to 3-6.

[0745] [Storage stability evaluation (1): foreign matter]

[0746] The obtained red photosensitive composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (EAGLE2000 manufactured by CORNING) using a spin coater to a film thickness of 2.5 μm after drying, and dried on a hot plate at 90° C. for 2 minutes. Then, after cooling to room temperature, an ultra-high pressure mercury lamp was used to illuminate the glass substrate at an illumination of 30 mW / cm 2 、100mJ / cm 2 Exposure was performed to prepare a cured film.

[0747] The number of foreign matter on the prepared cured film was measured, and the number of foreign matter on the obtained red photosensitive composition was less than 10. This was taken as the initial number of foreign matter. The measurement was performed using a metal microscope "BX60" (manufactured by OLYMPUS SYSTEM Co., Ltd.) with a magnification of 500 times, and the number of foreign matter observable in any five fields of view through transmission was accumulated for measurement.

[0748] The red photosensitive composition was placed in a sealed container and stored at 40°C for 10 days. The number of foreign matter after storage was measured under the same conditions as in the initial evaluation and evaluated based on the following criteria: 3 or more is practical.

[0749] 5: The amount of foreign matter after preservation is less than 110% of the initial amount of foreign matter

[0750] 4: The number of foreign matter after storage is 110% or more and less than 120% of the initial number of foreign matter

[0751] 3: The number of foreign matter after storage is 120% or more and less than 140% of the initial number of foreign matter

[0752] 2: The number of foreign matter after storage is 140% or more and less than 150% of the initial number of foreign matter

[0753] 1: The number of foreign matter after storage is more than 150% of the initial number of foreign matter

[0754] [Storage stability evaluation (2): film thickness]

[0755] The obtained red photosensitive composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (EAGLE2000 manufactured by CORNING) using a spin coater to a dry film thickness of 2.5 μm, and dried on a hot plate at 90°C for 2 minutes. Then, after cooling to room temperature, an ultra-high pressure mercury lamp was used to illuminate the film through a photomask with a 100 μm wide stripe pattern at an illumination of 30 mW / cm 2 、100mJ / cm 2 Expose. After cooling the substrate to room temperature, spray develop using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, wash with ion exchange water and air dry. After heating the obtained substrate at 90°C in a clean oven for 60 minutes, measure the film thickness of the pattern. This film thickness is taken as the initial film thickness.

[0756] The red photosensitive composition was placed in a sealed container and stored at 40° C. for 10 days. The film thickness after storage was measured under the same conditions as the initial film thickness, and the film thickness was defined as the film thickness after storage.

[0757] The film thickness change rate was calculated from the two film thicknesses by the following formula. The evaluation criteria were as follows: 3 or more was considered practical. The film thickness was the average value of 10 random locations measured using Dektak 3030 (manufactured by Japan Vacuum Technology Co., Ltd.).

[0758] Formula: Change rate (%) = |Film thickness after storage - initial film thickness| / initial film thickness × 100

[0759] 5: The rate of change is less than 3%

[0760] 4: The change rate is greater than 3% and less than 6%

[0761] 3: The change rate is greater than 6% and less than 10%

[0762] 2: The change rate is greater than 10% and less than 15%

[0763] 1: The change rate is more than 15%

[0764] [Developability Evaluation]

[0765] The obtained red photosensitive composition was applied to a glass substrate (EAGLE2000 manufactured by CORNING Co., Ltd.) with a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm using a spin coater to a dry film thickness of 2.5 μm, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of 100 μm in width at an illumination of 30 mW / cm 2 、100mJ / cm 2 Expose. After cooling the substrate to room temperature, spray develop using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, wash with ion exchange water, and air dry. Observe with an optical microscope to confirm the presence or absence of residue in the unexposed part. The evaluation criteria are as follows, 3 or more is practical.

[0766] 5: In the shortest development time that can form a pattern, there is no residue in the unexposed part.

[0767] 4: In the development for 5 seconds longer than the shortest time for pattern formation, no residue remains in the unexposed portion.

[0768] 3: In the development for 10 seconds longer than the shortest time for pattern formation, no residue remains in the unexposed portion.

[0769] 2: In the development for 15 seconds longer than the shortest time for pattern formation, no residue remains in the unexposed portion.

[0770] 1: Even in the development time which is 20 seconds longer than the shortest time which can form a pattern, there is a residue in the unexposed part.

[0771] [Pattern Formability Evaluation (1): Line Width]

[0772] The obtained red photosensitive composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (EAGLE2000 manufactured by CORNING) using a spin coater to a film thickness of 2.5 μm after drying, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate at an illumination of 30 mW / cm 2 , exposure 50mJ / cm 2 and 100mJ / cm 2The substrate was exposed at two levels through a photomask with a 100 μm wide stripe pattern. After the substrate was cooled to room temperature, it was spray developed using an aqueous developer containing 0.12% of a nonionic surfactant at 23°C and 0.04% of potassium hydroxide, washed with ion exchange water, and air-dried. The resulting substrate was heated at 90°C for 60 minutes in a clean oven to obtain an evaluation substrate. Spray development was performed on each red photosensitive composition within the shortest time that could form a pattern without development residue.

[0773] The obtained evaluation substrate was measured using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation at an exposure dose of 50 mJ / cm 2 Line width (CD 50 ) and 100mJ / cm 2 Line width (CD 100 ), and the difference in line width (ΔCd) caused by the difference in exposure amount was calculated by the following formula (1). The evaluation criteria were as follows, and 3 or more was considered practical.

[0774] Formula (1): ΔCd=CD 100 -CD 50

[0775] 5: ΔCd is less than 2μm

[0776] 4: ΔCd is greater than 2μm and less than 3μm

[0777] 3: ΔCd is 3 μm or more and less than 5 μm

[0778] 2: ΔCd is 5 μm or more and less than 6 μm

[0779] 1: ΔCd is 6μm or more

[0780] [Pattern Formability Evaluation (2): Linearity]

[0781] The obtained red photosensitive composition was applied to a glass substrate (EAGLE2000 manufactured by CORNING Co., Ltd.) with a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm using a spin coater to a dry film thickness of 2.5 μm, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of 100 μm in width at an illumination of 30 mW / cm 2 、100mJ / cm 2Exposure was performed. After the substrate was cooled to room temperature, it was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, and then washed with ion-exchanged water and air-dried. The obtained substrate was heated in a clean oven at 90°C for 60 minutes to obtain an evaluation substrate. Spray development was performed for each red photosensitive composition within the shortest time that could form a pattern without development residue.

[0782] The obtained substrate was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation and averaging the results. The evaluation criteria were as follows: 3 or more was considered practical.

[0783] 5: The difference between the maximum and minimum line width is less than 0.5μm

[0784] 4: The difference between the maximum and minimum line width is greater than 0.5 μm and less than 1.0 μm

[0785] 3: The difference between the maximum and minimum line width is 1.0μm or more and less than 1.5μm

[0786] 2: The difference between the maximum and minimum line width is 1.5μm or more and less than 2.0μm

[0787] 1: The difference between the maximum and minimum line width is 2.0μm or more

[0788] [High temperature and high humidity resistance evaluation]

[0789] The obtained red photosensitive composition was applied to a 100 mm × 100 mm, 0.7 mm thick glass substrate (EAGLE2000 manufactured by CORNING) using a spin coater to a film thickness of 2.5 μm after drying, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate at an illumination of 30 mW / cm 2 、100mJ / cm 2 After the substrate was cooled to room temperature, it was spray developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion exchange water and air-dried. The obtained substrate was post-baked in a clean oven at 90°C for 60 minutes to obtain an evaluation substrate.

[0790] The obtained substrate was stored for 200 hours at a temperature of 85°C and a humidity of 85%. After storage, a 1 mm square grid pattern (a total of 100 grids) was scratched on the film with a cutter, and a transparent adhesive tape (CT-24 made by NICHIBAN) was strongly pressed. After peeling in a direction of about 180 degrees, the state of the grid pattern was observed and the number of peeled grid patterns was counted. The evaluation criteria are as follows, and 3 or more is practical.

[0791] 5: Less than 2

[0792] 4: 2 or more and less than 5

[0793] 3: 5 or more and less than 10

[0794] 2: 10 or more and less than 15

[0795] 1: 15 or more

[0796] [Evaluation of solvent resistance]

[0797] The obtained red photosensitive composition was applied to a glass substrate (EAGLE2000 manufactured by CORNING Co.) with a length of 100 mm × a width of 100 mm and a thickness of 0.7 mm using a spin coater to a film thickness of 2.5 μm after drying, and dried on a hot plate at 90°C for 2 minutes. Then, after the substrate was cooled to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of 100 μm in width at an illumination of 30 mW / cm 2 、100mJ / cm 2 After the substrate was cooled to room temperature, it was spray developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, washed with ion exchange water, and air-dried. The obtained substrate was heated in a clean oven at 90°C for 60 minutes to obtain an evaluation substrate.

[0798] The obtained evaluation substrate was immersed in PGMAc at room temperature for 15 minutes, then washed with ion exchange water, air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria were as follows, and 3 or more was considered practical.

[0799] 5: No change in appearance or color

[0800] 4: Slight wrinkles, etc., but no color change

[0801] 3: Some wrinkles appear, but the color does not change

[0802] 2: Wrinkles and other problems occur on the entire surface, and there is a small amount of fading

[0803] 1: Peeling and fading [Table 3-1]

[0804]

[0805]

Table 3-2

[0806]

[0807]

Table 3-3

[0808]

[0809]

Table 3-4

[0810]

[0811]

Table 3-5

[0812]

[0813]

Table 3-6

[0814]

Claims

1. A red photosensitive composition comprising a color material (A), a resin having an acidic group (B), a polymerizable compound (C), and a polymerization initiator (D), wherein: The color material (A) includes a red color material (A1) and a yellow color material (A2), The red color material (A1) includes one or more selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264, The yellow color material (A2) comprises an isoindoline pigment, The polymerization initiator (D) contains propylene glycol monomethyl ether acetate, and the absorption coefficient of light with a wavelength of 365 nm is 5.0×10 3 The polymerization initiator (D1) has a polymerization amount of at least L / mol·cm.

2. The red photosensitive composition according to claim 1, wherein The red photosensitive composition further includes a thermally crosslinkable compound (E).

3. The red photosensitive composition according to claim 2, wherein The thermally crosslinkable compound (E) includes a compound (E2) having a blocked isocyanate group.

4. The red photosensitive composition according to claim 1, wherein The resin (B) having an acidic group includes a resin (B1) having an aromatic carboxyl group.

5. The red photosensitive composition according to claim 1, wherein The polymerization initiator (D1) comprises a polymerization initiator (D2) represented by the general formula (18), 【Chemistry 1】 General formula (18) In the general formula (18), R1 represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclicoxy group, a substituted or unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group; R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, or a substituted or unsubstituted aryl group; and R4 and R5 each independently represent a hydrogen atom, a halogen atom, a cyano group, or a nitro group.

6. The red photosensitive composition according to claim 3, wherein The thermally crosslinkable compound (E) includes a compound (E1) having an epoxy group.

7. The red photosensitive composition according to claim 6, wherein The mass ratio of the compound having an epoxy group (E1) to the compound having a blocked isocyanate group (E2) is 5:95 to 95:

5.

8. The red photosensitive composition according to claim 1, wherein The red photosensitive composition further includes an ultraviolet absorber (F).

9. The red photosensitive composition according to claim 1, wherein The red photosensitive composition further includes a pigment derivative (G) having basicity.

10. The red photosensitive composition according to claim 1, wherein The resin (B) having an acidic group includes a resin (B1) having an aromatic carboxyl group and a resin (B2) not having an aromatic carboxyl group.

11. The red photosensitive composition according to claim 1, wherein The color material (A) further includes one or more selected from the group consisting of a blue color material (A3) and a purple color material (A4).

12. The red photosensitive composition according to claim 11, wherein The blue color material (A3) includes at least one selected from the group consisting of CI pigment blue 15:3, CI pigment blue 15:4, CI pigment blue 15:6, and CI pigment blue 16.

13. The red photosensitive composition according to claim 11, wherein The purple color material (A4) includes a compound having a xanthene skeleton. 14 . A film formed from the red photosensitive composition according to claim 1 . A color filter comprising the film according to claim 14 . 16 . A solid-state imaging element comprising the color filter according to claim 15 .

17. An image display device comprising the color filter according to claim 15.

Images