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

Abstract

To provide a red photosensitive composition which enables formation of a film that is excellent in storage stability and has excellent resistance after low temperature heating.SOLUTION: A red photosensitive composition contains a coloring material (A), a resin (B) having an acidic group, a polymerizable compound (C), and a polymerization initiator (D), wherein the coloring material (A) contains a red coloring material (A1) and a yellow coloring material (A2), the red coloring material (A1) contains one or more kinds selected from the group consisting of C.I. pigment red 179 and C.I. pigment red 264, the yellow coloring material (A2) contains an isoindoline pigment, and the polymerization initiator (D) contains a polymerization initiator (D1) having absorption coefficient of light at a wavelength of 365 nm in propylene glycol monomethyl ether acetate of 5.0×103 L / mol cm or more.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a red photosensitive composition for use in the formation of a color filter for use in a solid-state imaging device, an image display device, or the like. [Background technology]

[0002] Color filters are generally produced by forming a pattern using a photolithography method. Photolithography involves, for example, a step of applying a photosensitive composition to a substrate such as glass, removing the solvent from the coating film by drying, a step of irradiating and curing the coating film with radiation through a photomask having a desired pattern shape (hereinafter referred to as exposure), a step of cleaning and removing the unexposed parts of the coating film (hereinafter referred to as development), and a step of heating the cured film to sufficiently cure it (hereinafter referred to as post-baking) to produce a pattern. Then, a color filter is completed by repeating the above steps multiple times.

[0003] Photosensitive compositions used in the manufacture of color filters are usually stored for several weeks to several months after manufacture before use, which can lead to problems such as the generation of foreign matter in the photosensitive composition during storage and the occurrence of variations in film thickness and pattern shape during pattern formation due to changes in the photosensitive composition over time.

[0004] In addition, the area per pixel tends to become smaller due to the miniaturization and high pixel density of image display devices and solid-state imaging devices, and color filters are required to be thinner. Therefore, the concentration of color materials contained in the pixels of the color filter becomes higher, and the amount of components other than the color materials becomes relatively smaller. As a result, there is a problem that the developability and pattern formability are deteriorated.

[0005] Furthermore, in recent years, from the viewpoint of environmental issues, there has been a demand to lower the temperature in the post-baking step, which has resulted in insufficient curing in the post-baking step, resulting in a problem of deterioration in resistance.

[0006] In order to solve these problems, for example, Patent Document 1 discloses a color filter colorant dispersion liquid that is excellent in colorant dispersion stability and can form a colored layer with improved contrast and color reproducibility while reducing the retardation value, and contains a colorant, a dispersant, and a solvent, in which the colorant contains a red colorant and a yellow colorant, the yellow colorant contains an anion of a specific azo compound and an azo compound having a tautomeric structure thereof, at least two specific metal ions, and a specific compound, and the dispersant contains a polymer having a specific structural unit. Patent Document 2 discloses an organic pigment composition for color filters that contains 1 to 15 parts of an organic dye derivative containing a sulfone group per 100 parts of a perylene organic pigment, and has a primary particle size of 20 to 100 nm, as an organic pigment composition for color filters with good dispersion stability. Patent Document 3 discloses a red pigment-dispersed resist composition for color filters having excellent dispersion stability and high coloring power and high brightness, the red pigment-dispersed resist composition for color filters containing CI Pigment Red 264, and one or more selected from CI Pigment Red 254, CI Pigment Red 177, and CI Pigment Red 179, a pigment dispersion obtained by adding and dispersing a pigment dispersing aid having a specific structure, a basic group-containing polymeric pigment dispersant, an alkali-soluble resin, and an organic solvent, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and an organic solvent.

[0007] Patent Document 4 discloses a colored photosensitive composition that can be cured under a low-temperature environment, the colored photosensitive composition containing a colorant, a polymerizable compound, and a photopolymerization initiator, the photopolymerization initiator being dissolved in acetonitrile at 0.001% by mass, and the absorbance at a wavelength of 340 nm of the solution is 0.45 or more. Patent Document 5 discloses a colored resin composition that contains a pigment, a resin, a polymerizable compound, and a polymerization initiator, the pigment including CI Pigment Violet 19, a red pigment, and a yellow pigment, as a colored resin composition that has excellent low-temperature curability and red color reproducibility. Patent Document 6 discloses a photosensitive resin composition that contains a resin having a constitutional unit having an α,β-unsaturated carbonyl group, a constitutional unit having an active methylene group or an active methine group, and a constitutional unit having an acid group, as a curable resin composition that can form a cured film having excellent solvent resistance and adhesion even when the temperature of the post-bake process is 200° C. or less. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2018 / 124087 [Patent Document 2] International Publication No. 2015 / 015962 [Patent Document 3] JP 2015-79161 A [Patent Document 4] International Publication No. 2017 / 038708 [Patent Document 5] International Publication No. 2021 / 131834 [Patent Document 6] Patent Publication No. 2022-10246 Summary of the Invention [Problem to be solved by the invention]

[0009] However, the compositions described in Patent Documents 1 to 6 could not satisfy all of the storage stability, developability, pattern formability, and film resistance after low-temperature heating at a constant level.

[0010] An object of the present invention is to provide a red photosensitive composition which is excellent in storage stability, developability and pattern formability and which is capable of forming a film having excellent resistance after low-temperature heating. [Means for solving the problem]

[0011] The present invention relates to a red photosensitive composition comprising a colorant (A), a resin having an acidic group (B), a polymerizable compound (C), and a polymerization initiator (D), the color material (A) contains a red color material (A1) and a yellow color material (A2); the red colorant (A1) comprises one or more selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264, The yellow colorant (A2) contains an isoindoline pigment, The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. 3 The present invention relates to a red-sensitive composition comprising a polymerization initiator (D1) having a photoinitiator activity of at least L / mol·cm. Effect of the Invention

[0012] According to the present invention, there can be provided a red photosensitive composition which is excellent in storage stability, developability, and pattern formability and is capable of forming a film having excellent resistance after low-temperature heating. The present invention also can provide a film, a color filter, a solid-state imaging device, and an image display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] Hereinafter, the embodiment for carrying out the red-sensitive composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiment, and can be modified within a range in which the problem can be solved.

[0014] In this specification, unless otherwise specified, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" means Color Index (CI; published by The Society of Dyers and Colourists). In this specification, a polymerizable unsaturated group is an ethylenically unsaturated double bond. As used herein, a monomer is a compound that will polymerize to form a resin. A monomer is in its unreacted state, and a monomer unit is a monomer that has been polymerized to form a resin. In this specification, the molecular weight of a low molecular weight compound that can be specified is a calculated value (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight of a compound having a molecular weight distribution is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits.

[0015] <Red photosensitive composition> A red photosensitive composition according to one embodiment of the present invention is a red photosensitive composition comprising a colorant (A), a resin having an acidic group (B), a polymerizable compound (C), and a polymerization initiator (D), the color material (A) contains a red color material (A1) and a yellow color material (A2); the red colorant (A1) comprises one or more selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264, The yellow colorant (A2) contains an isoindoline pigment, The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. 3 L / mol cm or more of a polymerization initiator (D1).

[0016] The mechanism by which the red photosensitive composition having the above-mentioned structure can solve the problems of the present invention is not clear, but is presumed to be as follows.

[0017] The red coloring material (A1), CI Pigment Red 179 and CI Pigment Red 264, have poor dispersion stability. Therefore, when a red photosensitive composition containing these red coloring materials (A1) is stored for a long period of time, foreign matter is likely to be generated due to association and aggregation between the red coloring materials (A1). However, it is presumed that by using an isoindoline pigment and a resin (B) having an acidic group, association and aggregation of the red coloring material (A1) during storage is suppressed, improving storage stability. In addition, compared to the case where a resin having a basic group is used, solubility in an alkaline aqueous solution is improved. Therefore, it is presumed that residues during development are suppressed and pattern formability is improved. And, as the polymerization initiator (D), a resin having an absorption coefficient of 5.0×10 for light having a wavelength of 365 nm in propylene glycol monomethyl ether acetate is used. 3 We speculate that by using a polymerization initiator (D1) with a polymerization activity of 1000 L / mol cm or more, the photoreaction is facilitated and the film resistance can be maintained at low temperature heating at the same level as at high temperature heating.

[0018] The components that are or can be included in the red-sensitive composition of the present invention are described in detail below.

[0019] Colorant The red photosensitive composition of the present invention contains a colorant (A).

[0020] The color material (A) is not particularly limited, and examples thereof include chromatic color materials such as red color materials, yellow color materials, blue color materials, purple color materials, green color materials, and orange color materials, achromatic color materials such as white color materials and black color materials, near-infrared absorbing color materials, and fluorescent color materials. In this specification, the white colorant includes not only pure white but also light gray colorants close to white (for example, grayish white, light gray). The coloring material (A) may be either a pigment or a dye, or a pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, or an inorganic pigment and an organic pigment may be used in combination. Further, examples of the pigment include an organic-inorganic composite.

[0021] The pigment is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle size is more preferably 10 to 70 nm.

[0022] The content of the color material (A) is preferably from 0.5 to 60 mass %, and more preferably from 1 to 50 mass %, based on 100 mass % of the nonvolatile content of the red photosensitive composition.

[0023] (Red color material (A1)) The red photosensitive composition of the present invention contains a red colorant (A1), and contains at least one member selected from the group consisting of CI Pigment Red 179 and CI Pigment Red 264 as the red colorant (A1).

[0024] The red colorant (A1) preferably contains CI Pigment Red 264 from the viewpoint of light fastness.

[0025] The total content of CI Pigment Red 179 and CI Pigment Red 264 is preferably from 60 to 100% by mass, and more preferably from 80 to 100% by mass, in 100% by mass of the red colorant (A1).

[0026] The red colorant (A1) may contain red colorants other than CI Pigment Red 179 and CI Pigment Red 264.

[0027] The red coloring material other than CI Pigment Red 179 and CI Pigment Red 264 is not particularly limited, and known compounds can be used. 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 ,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262 , 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, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Further examples include 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, as well as lake compounds, salt-forming compounds, and polymers of these red dyes.

[0028] The content of the red color material (A1) is preferably from 60 to 99 mass %, and more preferably from 70 to 95 mass %, in 100 mass % of the color material (A).

[0029] (Yellow color material (A2)) The red photosensitive composition of the present invention contains a yellow colorant (A2), and contains an isoindoline pigment as the yellow colorant (A2).

[0030] The isoindoline pigment is not particularly limited, and known compounds can be used. For example, CI Pigment Yellow 109, 110, 137, 139, 173, 177, 179, 185, and pigments described in JP-A-2011-025194 and JP-A-2022-025209 can be mentioned. Among these, from the viewpoint of storage stability, CI Pigment Yellow 139 and 185 are preferred, and CI Pigment Yellow 139 is more preferred.

[0031] The content of the isoindoline pigment is preferably from 60 to 100 mass %, and more preferably from 80 to 100 mass %, in 100 mass % of the yellow color material (A2).

[0032] The yellow colorant (A2) can contain a yellow colorant other than an isoindoline pigment.

[0033] The yellow coloring material other than the isoindoline pigment is not particularly limited, and known compounds can be used. 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, 126 , 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, and the yellow pigments described in JP-A-2012-226110.

[0034] Further, examples of yellow pigments include metal azo pigments containing one or more anions selected from the group consisting of azo compounds represented by the following general formula (1) and mono-, di-, tri-, and tetraanions of azo compounds having a tautomeric structure thereof, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (2).

[0035] General formula (1) [ka]

[0036] In general formula (1), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and two R2s each independently represent -OH or -NH2.

[0037] General formula (2) [ka]

[0038] In general formula (2), three R3's each independently represent a hydrogen atom or an alkyl group.

[0039] 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.

[0040] Further examples include 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, yellow dyes having a methine structure described in JP-A-2019-073695, JP-A-2019-073696, JP-A-2019-073697, and JP-A-2019-073698, as well as lake compounds, salt-forming compounds, and polymers of these yellow dyes.

[0041] The content of the yellow color material (A2) is preferably from 1 to 40 mass %, and more preferably from 5 to 30 mass %, in 100 mass % of the color material (A).

[0042] The red photosensitive composition of the present invention may contain, as the colorant (A), a colorant other than the red colorant (A1) and the yellow colorant (A2).

[0043] The coloring materials other than the red coloring material (A1) and the yellow coloring material (A2) are not particularly limited, and known compounds can be used. For example, chromatic coloring materials such as blue coloring materials, purple coloring materials, green coloring materials, and orange coloring materials, white coloring materials, and black coloring materials can be used. Among these, from the viewpoint of spectral characteristics, it is preferable that the coloring materials other than the red coloring material (A1) and the yellow coloring material (A2) include one or more types selected from the group consisting of the blue coloring material (A3) and the purple coloring material (A4).

[0044] (Blue color material (A3)) The blue colorant (A3) is not particularly limited, and known compounds can be used. For example, blue pigments such as 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, and 88 can be mentioned. Further examples include 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 lake compounds, salt-forming compounds, and polymers of these blue dyes. Among these, from the viewpoint of light fastness, the blue colorant (A3) is preferably one or more 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.

[0045] The content of the blue color material (A3) is preferably from 0.1 to 15 mass %, and more preferably from 0.5 to 10 mass %, in 100 mass % of the color material (A).

[0046] (Purple color material (A4)) The purple colorant (A4) is not particularly limited, and any known compound can be used. Examples of the purple pigment include CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61. Further examples include 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, and CI Acid Red 51, 52, 87, 92, 94, 289, 388, and 463; and lake compounds, salt-forming compounds, and polymers of these compounds. Among these, from the viewpoint of luminance, the purple color material (A4) is preferably a compound having a xanthene skeleton.

[0047] The compound having a xanthene skeleton is not particularly limited as long as it has a xanthene skeleton, and known compounds can be used. For example, compounds described in JP 2012-013758 A, JP 2012-208452 A, JP 2013-033194 A, WO 2016 / 031442 A, WO 2016 / 121194 A, JP 2019-109490 A, WO 2019 / 031292 A, etc. can be mentioned. 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 and a resin that forms a salt with these dyes.

[0048] The content of the purple color material (A4) is preferably from 0.1 to 15 mass %, and more preferably from 0.5 to 10 mass %, in 100 mass % of the color material (A).

[0049] [Resin having acidic groups (B)] The red photosensitive composition of the present invention contains a resin (B) having an acidic group.

[0050] The resin (B) having an acidic group is used for the purpose of stably dispersing the coloring material (A) and for the purpose of imparting resistance to the film. The resin (B) having an acidic group that is mainly used to disperse the coloring material (A) is also called a dispersion resin, and the resin (B) having an acidic group that is mainly used to impart resistance to the film is also called a binder resin. The resin (B) having an acidic group may have the functions of both a dispersion resin and a binder resin in one resin. However, such use of the resin (B) having an acidic group is only an example, and it can also be used for other purposes. In this specification, the resin (B) having an acidic group refers to a resin in which the amount of acidic groups is greater than the amount of basic groups.

[0051] Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. Among these, from the viewpoint of storage stability, a carboxyl group and a phosphoric acid group are preferred.

[0052] The acid value of the resin (B) having an acidic group is preferably from 30 to 250 mgKOH / g, more preferably from 40 to 200 mgKOH / g.

[0053] The weight average molecular weight of the resin (B) having an acidic group is preferably from 2,000 to 50,000, and more preferably from 4,000 to 40,000.

[0054] The resin (B) having an acidic group can be used alone or in combination of two or more kinds.

[0055] The content of the resin (B) having an acidic group is preferably from 1 to 60 mass %, and more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the red photosensitive composition.

[0056] (Resin having an aromatic carboxyl group (B1)) From the viewpoint of storage stability, the resin (B) having an acidic group preferably contains 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 have a strong interaction with the aromatic carboxyl group. It is presumed that the resin (B1) having an aromatic carboxyl group is not separated from the colorant (A) during storage, and the dispersion stability of the colorant (A) is maintained. In this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring.

[0057] The aromatic carboxyl group may be contained in the main chain or in a side chain of the resin, but is preferably contained in the main chain from the viewpoint of storage stability.

[0058] The number of carboxyl groups bonded to the aromatic ring of the aromatic carboxyl group is preferably 1 to 4 from the viewpoint of storage stability.

[0059] From the viewpoint of storage stability, the resin (B1) having an aromatic carboxyl group preferably contains a resin having a main chain based on an aromatic carboxylic acid ester moiety having an ester bond, which is a reaction product site between an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain based on a vinyl polymer moiety.

[0060] The aromatic carboxylate moiety in 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 at the same time as the ester bond is generated. The aromatic carboxyl group acts as an adsorption site for the colorant (A).

[0061] The vinyl polymer moiety in the side chain acts as a steric repulsion moiety and suppresses the association and aggregation of the colorant (A). The vinyl polymer moiety in the side chain can be obtained, for example, by the following two methods. 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. The second method is a method in which a monomer is copolymerized in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and a hydroxyl group of a compound having two or more hydroxyl groups. The difference between the above two methods is whether the vinyl polymer moiety is introduced first or later by copolymerizing the monomer. The molecular weight may differ slightly depending on various conditions, but in theory, the same compound can be synthesized if the raw materials and reaction conditions are the same.

[0062] The main chain and the side chain will be described in detail below.

[0063] [Main Chain] The aromatic carboxylate moiety can be 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.

[0064] Examples of aromatic compounds having two or more acid anhydride groups include compounds represented by the following general formulas (3) and (4).

[0065] [ka]

[0066] In formula (3), n represents 1 or 2. In 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).

[0067] [ka]

[0068] Specific examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 2,3,6,7-naphthalene tetracarboxylic dianhydride. 3,3',4,4'-Dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-Furanetetracarboxylic dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-Bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride Anhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether tert-butyl dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Among these, aromatic tetracarboxylic acid dianhydrides are preferred, and pyromellitic dianhydride is more preferred.

[0069] 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.

[0070] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0071] From the viewpoint of storage stability, the aromatic carboxylate moiety is preferably a reaction product site of 0.9 to 1.5 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. More preferably, it is a reaction product site of 1.0 to 1.3 moles of an aromatic compound having two or more acid anhydride groups per mole of a compound having two or more hydroxyl groups. Storage stability is improved by increasing the proportion of aromatic carboxyl groups, which are adsorption sites to the coloring material (A). Theoretically, when the aromatic compound having two or more acid anhydride groups exceeds 1 mole, the terminal becomes an acid anhydride group.

[0072] In addition, the acid anhydride group present at the end of the aromatic carboxylic acid ester moiety may be reacted with a monoalcohol. That is, the acid anhydride group is ring-opened with the monoalcohol to generate an alcohol ester and a carboxyl group. This improves the solubility in the developer and improves the developability. Note that a monoamine can be used instead of the monoalcohol.

[0073] Examples of the monoalcohol include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; Examples of the lactate include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. Among these, 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 monoalcohols may be used alone or in combination of two or more kinds.

[0074] The amount of 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.

[0075] [Side Chain] As described above, the vinyl polymer segment can be synthesized by a method of copolymerizing a monomer in the presence of a compound having two or more hydroxyl groups, or a method of copolymerizing a monomer in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and hydroxyl groups of a compound having two or more hydroxyl groups.

[0076] Examples of the monomer include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, and the like. ) acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, or 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, or other linear or branched alkyl (meth)acrylates; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); (meth)acrylates having a heterocycle, such as tetrahydrofurfuryl (meth)acrylate or 3-methyl-3-oxetanyl (meth)acrylate; (meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (meth)acrylates having a carboxyl group, such as (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate; Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; 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; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitriles such as (meth)acrylonitrile; 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; vinyl acetate, vinyl propionate and other vinyl fatty acids; Examples of the monomer include acidic group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0077] From the viewpoint of film resistance after low-temperature heating, the vinyl polymer portion preferably has a thermally crosslinkable group and / or a polymerizable unsaturated group. Examples of the thermally crosslinkable group include a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group. A thermally crosslinkable group can be introduced by using a monomer having a hydroxyl group, an epoxy group, an oxetanyl group, a tert-butyl group, a blocked isocyanate group, or the like. The polymerizable unsaturated group can be introduced, for example, by reacting a hydroxyl group present in the vinyl polymer moiety with an isocyanate group of a monomer having an isocyanate group.

[0078] A preferred method for synthesizing the resin (B1) having an aromatic carboxyl group is, for example, to radically polymerize a monomer in the presence of a compound (a) having two hydroxyl groups and one thiol group at one end, which is a compound having two or more hydroxyl groups, to generate a vinyl polymer having two hydroxyl groups at one end, and then react the resulting polymer with a tetracarboxylic dianhydride (b), which is an aromatic compound having two or more acid anhydride groups. Furthermore, when the end of the resin is an acid anhydride group, a blocking moiety derived from the monoalcohol can be introduced by reacting the resin with a monoalcohol.

[0079] [ka]

[0080] In (c), X is the reaction residue after the tetracarboxylic dianhydride (b) reacts with a hydroxyl group, Z is the reaction residue after a compound having two hydroxyl groups reacts with an acid anhydride group, and R is the residue of a monoalcohol.

[0081] The polymerization temperature of the vinyl polymer portion is preferably 40 to 150° C., more preferably 50 to 110° C. If it is 40° C. or higher, the polymerization proceeds easily, and if it is 150° C. or lower, it becomes easy to control the molecular weight.

[0082] When polymerizing the vinyl polymer portion, 0.001 to 5% by mass of a polymerization initiator can be used based on the total monomer mass of the monomers. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0083] 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), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane]. Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide. The polymerization initiators can be used alone or in combination of two or more.

[0084] The vinyl polymer portion is preferably synthesized by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include, but are not limited to, 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, and diethylene glycol monobutyl ether acetate. These polymerization solvents can be used alone or in combination of two or more.

[0085] A reaction catalyst can be used for the synthesis of the aromatic carboxylate moiety. The reaction catalyst is preferably a tertiary amine compound. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0086] For the synthesis of the aromatic carboxylate moiety, 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.

[0087] The synthesis temperature for the aromatic carboxylate moiety is preferably from 50 to 180°C, more preferably from 80 to 140°C.

[0088] The acid value of the resin (B1) having an aromatic carboxyl group is preferably from 20 to 250 mgKOH / g, more preferably from 30 to 200 mgKOH / g.

[0089] The weight average molecular weight of the resin (B1) having an aromatic carboxyl group is preferably from 2,000 to 40,000, and more preferably from 4,000 to 30,000.

[0090] The resin (B1) having an aromatic carboxyl group can be used alone or in combination of two or more kinds.

[0091] From the viewpoint of storage stability, the amount of the resin (B1) having an aromatic carboxyl group is preferably from 1 to 60 mass %, and more preferably from 5 to 50 mass %, in 100 mass % of the resin (B) having an acidic group.

[0092] (Resin not having an aromatic carboxyl group (B2)) From the viewpoint of film resistance after low-temperature heating, the resin (B) having an acidic group preferably contains a resin (B2) not having an aromatic carboxyl group as a binder resin in addition to the resin (B1) having an aromatic carboxyl group.

[0093] The resin (B2) having no aromatic carboxyl group is not particularly limited as long as it has no aromatic carboxyl group as an acidic group, and known resins can be used, such as (meth)acrylic resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, and cyclic olefin resin.

[0094] From the viewpoint of film resistance after low-temperature heating, the resin (B2) that does not have an aromatic carboxyl group is preferably a resin having a thermal crosslinking group-containing monomer unit and an acid group-containing monomer unit (excluding monomer units having an aromatic carboxyl group). The thermal crosslinking group is a group that undergoes a crosslinking reaction by heating and crosslinks. Examples of the thermal crosslinking group include a cyclic ether group, a methylol group, an isocyanate group, a blocked isocyanate group, an acetoacetoxy group, an alkoxysilyl group, and a tertiary alkyl group. A resin having a thermally crosslinkable group-containing monomer unit and an acid group-containing monomer unit other than an aromatic carboxyl group is synthesized, for example, by copolymerizing a thermally crosslinkable group-containing monomer, an acid group-containing monomer other than an aromatic carboxyl group, and any other copolymerizable monomer.

[0095] From the viewpoints of storage stability and resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit is preferably formed from a monomer represented by the following general formulas (7) to (11).

[0096] General formula (7) [ka]

[0097] In general formula (7), R 1 represents a hydrogen atom or a methyl group.

[0098] In general formula (7), R 2 and R 3 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0099] In general formula (7), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0100] In general formula (7), L 2 represents a single bond or an oxygen atom.

[0101] In general formula (7), L 3 and L 4 each independently represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene groups. Among these, methylene, ethylene, and n-propylene groups are preferred.

[0102] The method for producing the monomer represented by the general formula (7) is not particularly limited, and a known method can be used. For example, the methods described in JP-A-10-316643 and WO 2022 / 145298 can be mentioned.

[0103] Specific examples of the monomer represented by formula (7) include compounds of formulas (7-1) to (7-10), although the present invention is not limited thereto.

[0104] [ka]

[0105] From the viewpoint of resistance after low-temperature heating, the monomer represented by general formula (7) is preferably one or more selected from the compounds represented by the above formulae (7-1), (7-2), (7-3), (7-4), (7-9), and (7-10).

[0106] The monomer represented by formula (7) can be used alone or in combination of two or more kinds.

[0107] General formula (8) [ka]

[0108] In general formula (8), R 1 represents a hydrogen atom or a methyl group.

[0109] In general formula (8), R 4 ~R 6 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or a combination thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, R 4 and R 5 is preferably a hydrogen atom, R 6 is preferably a methyl group, an ethyl group, or an n-propyl group.

[0110] In general formula (8), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0111] 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.

[0112] Specific examples of the monomer represented by formula (8) include compounds represented by formulas (8-1) to (8-6), although the present invention is not limited thereto.

[0113] [ka]

[0114] The monomer represented by the general formula (8) can be used alone or in combination of two or more kinds.

[0115] General formula (9) [ka]

[0116] In general formula (9), R 1 represents a hydrogen atom or a methyl group.

[0117] In general formula (9), R 7 represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, methyl, ethyl, and n-propyl groups are preferred.

[0118] In general formula (9), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0119] The method for producing the monomer represented by the general formula (9) is not particularly limited, and a known method can be used, for example, the method described in Coatings Technology, Vol. 62, by Witzeman, JS, and Dell Rector, FJ.

[0120] Specific examples of the monomer represented by formula (9) include compounds represented by formulas (9-1) to (9-4), although the present invention is not limited thereto.

[0121] [ka]

[0122] The monomer represented by formula (9) can be used alone or in combination of two or more kinds.

[0123] General formula (10) [ka]

[0124] In general formula (10), R 1 represents a hydrogen atom or a methyl group.

[0125] In 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 10At least one of them is an alkoxy group having 1 to 6 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a butyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, and an isobutyl group. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, etc. Among these, from the viewpoint of resistance after low-temperature heating, a methoxy group and an ethoxy group are preferred. From the viewpoint of resistance after low-temperature heating, R 8 ~R 10 At least two of them are preferably alkoxy groups having 1 to 6 carbon atoms.

[0126] In general formula (10), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, or an alkylene group having 1 to 20 carbon atoms having -O- between the carbon-carbon bonds. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0127] Specific examples of the monomer represented by formula (10) include compounds of formulas (10-1) to (10-6), although the present invention is not limited thereto.

[0128] [ka]

[0129] Commercially available products of the monomer represented by the general formula (10) include, for example, KBM-502, 503, 5103, 5803, KBE-502, 503, and the like manufactured by Shin-Etsu Silicones.

[0130] The monomer represented by the general formula (10) can be used alone or in combination of two or more kinds.

[0131] General formula (11) [ka]

[0132] In general formula (11), R 1 represents a hydrogen atom or a methyl group.

[0133] In general formula (11), R 11 ~R 13 each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, isopropyl, isobutyl, amyl, isoamyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, and decyl groups. Among these, the methyl group is preferred.

[0134] In general formula (11), L 1 represents a single bond or a divalent organic group. The divalent organic group may be an alkylene group having 1 to 20 carbon atoms, a group having --NH--, or a combination thereof. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof. Examples include methylene, ethylene, n-propyl, n-butylene, n-pentylene, n-hexylene, n-heptylene, n-octylene, isopropylene, 2-methylpropylene, 2-methylhexylene, and tetramethylethylene. Among these, methylene, ethylene, and n-propylene are preferred.

[0135] Specific examples of the monomer represented by formula (11) include compounds represented by formulas (11-1) to (11-6), although the present invention is not limited thereto. [ka]

[0136] The monomer represented by the general formula (11) can be used alone or in combination of two or more kinds.

[0137] From the viewpoints of storage stability and resistance after low-temperature heating, the thermally crosslinkable group-containing monomer unit is more preferably formed from one or more of the monomer represented by general formula (7) and the monomer represented by general formula (8).

[0138] The thermally crosslinkable group-containing monomer unit can be formed by using the monomers represented by the general formulas (7) to (11) alone or in combination of two or more kinds.

[0139] The thermally crosslinkable group-containing monomer unit may be a combination of a monomer unit formed of a monomer represented by any one of the general formulae (7) to (11) and a monomer unit formed of a monomer other than the monomer represented by any one of the general formulae (7) to (11).

[0140] Examples of the monomer other than the monomers represented by the general formulas (7) to (11) include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (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]ethyl (meth)acrylate, 2-[O-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, and the like.

[0141] The content of the thermally crosslinkable group-containing monomer unit is preferably 1 to 80 mol %, more preferably 5 to 70 mol %, of all monomer units in the resin, from the viewpoints of storage stability and resistance after low-temperature heating.

[0142] Examples of the acid group-containing monomer (excluding 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-methacryloyloxyethyl succinic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate. The acidic group-containing monomers can be used alone or in combination of two or more kinds.

[0143] The method for introducing an acidic group may be a method of copolymerizing a thermocrosslinkable group-containing monomer with an acidic group-containing monomer, or a method of adding an acid anhydride (modifying compound) to a hydroxyl group contained in a resin (precursor). Examples of the acid anhydride include succinic anhydride, phthalic anhydride, and 1,2,3,6-tetrahydrophthalic anhydride.

[0144] The content of the acidic group-containing monomer unit in all the constituent units of the resin is preferably from 1 to 40 mol %, and more preferably from 5 to 30 mol %.

[0145] The copolymer may contain monomer units other than the thermally crosslinkable group-containing monomer units and the acidic group-containing monomer units (hereinafter, other monomer units).

[0146] Examples of monomers forming other monomer units include 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 phthalate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, ) 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, lauryl (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, EO or PO-modified (meth)acrylate of paracumylphenol, 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, and isobutyl vinyl ether, vinyl acetate, vinyl propionate, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, dimethy Examples of the aryl 2,2'-[oxybis(methylene)]bis-2-propenoate include diethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0147] The acid value of the resin (B2) having no aromatic carboxyl group is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0148] The weight average molecular weight of the resin (B2) having no aromatic carboxyl group is preferably from 3,000 to 50,000, and more preferably from 3,000 to 20,000.

[0149] The resin (B2) having no aromatic carboxyl group can be used alone or in combination of two or more kinds.

[0150] The content of the resin (B2) having no aromatic carboxyl group is preferably 30 to 95 mass % in 100 mass % of the resin (B) having an acidic group, from the viewpoint of resistance after low-temperature heating.

[0151] [Polymerizable compound (C)] The red photosensitive composition of the present invention contains a polymerizable compound (C).

[0152] 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, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group having an ethylenically unsaturated double bond.

[0153] The polymerizable compound (C) is not particularly limited, and a known compound can be used. For example, a polymerizable compound (C1) having an amine structure, a polymerizable compound (C2) having a hydroxyl group, a polymerizable compound (C3) having a dendrimer structure or a hyperbranch 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) can be mentioned.

[0154] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0155] The content of the polymerizable compound (C) is preferably from 1 to 80 mass %, and more preferably from 5 to 70 mass %, based on 100 mass % of the nonvolatile content of the red photosensitive composition.

[0156] (Polymerizable compound (C1) having an amine structure) The amine structure of the polymerizable compound (C1) having an amine structure includes primary amines, secondary amines, and tertiary amines. Among these, secondary amines and tertiary amines are preferred. However, the amine structure of the polymerizable compound (C1) having an amine structure does not include an amide structure, an imide structure, or a urethane structure in which a carbonyl group is directly bonded to a nitrogen atom.

[0157] Examples of the polymerizable compound (C1) having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, and tris(2-hydroxy-3-methacryloyloxypropyl)amine, as well as a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y).

[0158] Examples of the (meth)acrylate compound (X) include glycerin 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, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, penta ...hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol hexa(meth)acrylate, diglycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples of the alkylene oxide-modified tetra(meth)acrylate include phosphorus tri(meth)acrylate, diglycerol 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, diglycerol alkylene oxide-modified tri- and tetra(meth)acrylate, and dipentaerythritol alkylene oxide-modified tetra-, penta- and hexa(meth)acrylate. Examples of the alkylene oxide unit in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. The (meth)acrylate compound (X) also includes a (meth)acrylate compound having an acidic group.

[0159] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0160] 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; Examples of the secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilinephenol, and 4-anilinephenol.

[0161] The amine compound (Y) can be used alone or in combination of two or more kinds.

[0162] 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, the methods described in International Publication No. 2006 / 075754, JP-A-2008-545859, JP-A-2017-066347, etc. can be mentioned.

[0163] The polymerizable compound (C1) having an amine structure may have an acidic group and / or a hydroxyl group. Examples of a method 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 in the (meth)acrylate compound (X) or the amine compound (Y), and a method of adding an acid anhydride after the Michael addition reaction.

[0164] Commercially available polymerizable compounds (C1) having an amine structure include, for example, ARONIX MT-3041 and 3042 manufactured by Toagosei Co., Ltd., EBECRYL 80 and 7100 manufactured by Daicel-Allnex Corporation, and CN371NS, 372, 374, 383 and 386 manufactured by Arkema.

[0165] The polymerizable compound (C1) having an amine structure can further have a urethane bond. This forms a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between the urethane bonds and between the urethane bonds and the functional groups of the substrate. The molecular cohesive energy of the intermolecular hydrogen bonds in the urethane bonds is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes flexible and strong due to the interaction between the urethane bonds, improving its resistance.

[0166] The urethane bond can be introduced, for example, by a urethane reaction between 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).

[0167] 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; 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(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the polyisocyanate compound include polyisocyanate compounds having an aromatic structure, such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further, biuret, isocyanurate, adduct and allophanate forms of these compounds are also included.

[0168] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0169] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2018-517797 can be mentioned.

[0170] (Polymerizable compound having a hydroxyl group (C2)) 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, EO isocyanuric acid, or the like. Examples of the acrylic acid ester include PO-modified (meth)acrylate, isocyanuric acid EO or PO-modified di(meth)acrylate, 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, and epoxy (meth)acrylate obtained by reacting an epoxy group of an epoxy compound with a carboxyl group of (meth)acrylic acid. Among these, glycerol di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate are preferred.

[0171] Examples of commercially available polymerizable compounds (C2) having a hydroxyl group include KAYARAD R-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, Epoxy Ester M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A manufactured by Kyoeisha Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.

[0172] (Polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure) A compound having a dendrimer structure has a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, and a polymerizable unsaturated group is bonded to the end of the branch, and the compound has a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of the dendrimer structure.

[0173] Commercially available polymerizable compounds (C3) having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) and SIRUS-501 (dendrimer structure, average number of acryloyl groups: 18) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and SP-1108 (dendrimer 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 Examples include 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), and DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all manufactured by Materials.

[0174] (Polymerizable compound having an acidic group (C4)) The polymerizable compound (C4) having an acidic group is a compound having a molecular weight of 100 or more, and examples thereof include an esterification product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid with a dicarboxylic acid; an esterification product of a polycarboxylic acid with a monohydroxyalkyl (meth)acrylate, and the like.

[0175] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0176] Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0177] Examples of the polyvalent carboxylic acid include trimellitic acid and pyromellitic acid. Examples of 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.

[0178] 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-Allnex Corporation.

[0179] (Polymerizable compound having a urethane bond (C5)) Examples of the polymerizable compound (C5) having a urethane bond include urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the polyhydric alcohol with a hydroxyl group-containing (meth)acrylate.

[0180] 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 carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0181] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate, as well as biuret forms, isocyanurate forms, and trimethylolpropane adducts thereof.

[0182] 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 these, the carboxyl group is preferred.

[0183] The method for introducing an acidic group into the polymerizable compound (C5) having a urethane bond can be, for example, synthesized by first reacting the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the product.

[0184] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0185] Commercially available polymerizable compounds (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-Allnex Corporation.

[0186] (Lactone-modified polymerizable compound (C6)) 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 polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, or trimethylolmelamine with (meth)acrylic acid and ε-caprolactone or another lactone compound.

[0187] Commercially available lactone-modified polymerizable compounds (C6) include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0188] (Other polymerizable compounds (C7)) 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, isocyanuric acid. Examples of the methacrylic acid ester include EO- or PO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO- or PO-modified hexa(meth)acrylate, tricyclodecanyl (meth)acrylate, and (meth)acrylic acid ester of methylolated melamine; styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0189] Other commercially available polymerizable compounds (C7) include, for example, KAYARAD NPGDA, 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, and D-310 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, and M-21 manufactured by Toagosei Co., Ltd. 1B, 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 Organic Chemical Industry Co., Ltd., OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples of such esters include EA-0200, EA-0300, Miramer HR6060, 6100, and 6200 manufactured by Miwon Specialty Chemical Co., Ltd., and 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, and AD-TMP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0190] Further examples include (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.

[0191] From the viewpoint of resistance after low-temperature heating, the polymerizable compound (C) preferably contains one or more compounds 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 dendrimer structure or a hyperbranched structure.

[0192] 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 dendrimer structure or a hyperbranched structure is preferably 10 to 100 mass%, and more preferably 20 to 100 mass%, in 100 mass% of the polymerizable compound (C).

[0193] [Polymerization initiator (D)] The red photosensitive composition of the present invention contains a polymerization initiator (D).

[0194] The polymerization initiator (D) is not particularly limited, and any known compound can be used. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction can be used. The polymerization initiator that generates radicals by light (hereinafter, also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals by light rays in the ultraviolet to visible light range. The polymerization initiator that generates radicals by heat (hereinafter, also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0195] Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; and carbazole-based compounds.

[0196] Commercially available products include 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 Arcles N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples of such adhesives include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemistrys. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855 A, JP 2022-5115524 A, WO 2023 / 085056 A, etc. are also included.

[0197] Examples of the thermal polymerization initiator include 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, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol compounds such as 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; Additionally, the azo compounds and organic peroxides already explained can also be used.

[0198] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0199] The content of the polymerization initiator (D) is preferably from 0.1 to 20 mass %, and more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the red photosensitive composition.

[0200] (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) The red photosensitive composition of the present invention contains a polymerization initiator (D) having an absorption coefficient of 5.0×10 3 L / mol cm or more of a polymerization initiator (D1) (hereinafter simply referred to as polymerization initiator (D1)).

[0201] The absorption coefficient of the polymerization initiator (D1) in propylene glycol monomethyl ether acetate at a wavelength of 365 nm is 5.0 × 10 3 ~5.0×10 4 mL / gcm is preferred, 1.0×10 4 ~4.0×10 4 L / mol·cm is more preferred.

[0202] The polymerization initiator (D1) is not particularly limited, and known compounds can be used. For example, compounds described in International Publication No. 2008 / 078678, JP 2009-134289 A, Japanese Patent No. 4600600 A, JP 2011-132215 A, JP 2014-500852 A, JP 2015-523318 A, International Publication No. 2015 / 036910 A, International Publication No. 2017 / 051680 A, International Publication No. 2021 / 175855 A, and JP 2022-515524 A can be mentioned. Among these, compounds having one oxime ester group are preferred, and compounds having two oxime ester groups are more preferred. By having two oxime ester groups, the radical generating ability is high and it is less susceptible to oxygen inhibition. This promotes photocuring and improves resistance to low-temperature heating.

[0203] Specific examples of the polymerization initiator (D1) are shown below, but the present invention is not limited to these.

[0204] [ka]

[0205] [ka]

[0206] The polymerization initiator (D1) can be used alone or in combination of two or more kinds.

[0207] The content of the polymerization initiator (D1) is preferably from 10 to 100 mass%, and more preferably from 20 to 100 mass%, in 100 mass% of the polymerization initiator (D).

[0208] [Thermal crosslinkable compound (E)] The red photosensitive composition of the present invention preferably contains a thermally crosslinkable compound (E) from the viewpoint of resistance after low-temperature heating. This allows the thermally crosslinkable compound (E) to crosslink upon heating, improving resistance. In this specification, the thermally crosslinkable compound (E) does not have an acidic group or a polymerizable unsaturated group, and is therefore different from the resin (B) and polymerizable compound (C) that have an acidic group.

[0209] The thermal crosslinking compound (E) is not particularly limited as long as it is a compound having a thermal crosslinking group, and a known compound can be used. For example, a compound having an epoxy group, a compound having a blocked isocyanate group, a compound having an oxetanyl group, a compound having a methylol group, a compound having a phenol group, a compound having an alkoxyalkyl group, etc. can be mentioned. Among these, it is preferable to include at least one selected from the group consisting of a compound having an epoxy group and a compound having a blocked isocyanate group.

[0210] The thermally crosslinkable compound (E) can be used alone or in combination of two or more kinds.

[0211] The content of the thermally crosslinkable compound (E) is preferably from 0.5 to 40 mass %, and more preferably from 1 to 30 mass %, based on 100 mass % of the nonvolatile content of the red photosensitive composition.

[0212] (Compound (E1) having an epoxy group) The thermally crosslinkable compound (E) preferably contains a compound (E1) having an epoxy group, whereby the epoxy group is crosslinked by heating, and resistance is further improved.

[0213] The epoxy group is a group having a three-membered cyclic ether structure, including 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; Polyglycidyl ether compounds of polyhydric alcohols, such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding alkylene oxides to polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin; 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 bis(3,4-epoxycyclohexylmethyl)-5,5-spiro-3,4-epoxy)cyclohexane-metadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexane), ethylene bis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylate tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone; Examples include an adduct of 2,2-bis(hydroxymethyl)-1-butanol with 1,2-epoxy-4-(2-oxiranyl)cyclohexane.

[0214] Commercially available products of the compound (E1) having an epoxy group include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150, Epolead GT401 manufactured by Daicel Chemical Industries, Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, and EPICLON manufactured by DIC Corporation Examples include 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, and HP-9500.

[0215] The compound (E1) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0216] 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 an epoxy compound containing one equivalent of an epoxy group.

[0217] From the viewpoint of resistance after low-temperature heating, the compound (E1) having an epoxy group more preferably contains a compound represented by the following general formula (12).

[0218] General formula (12) [ka]

[0219] In formula (12), R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol, m represents an integer of 1 to 6, and n represents an integer of 1 to 30.

[0220] R represents a group obtained by removing m hydroxyl groups from an m-hydric alcohol. The group obtained by removing m hydroxyl groups from the m-hydric alcohol is preferably an alkyl group having 2 to 20 carbon atoms, and may be linear, branched, or cyclic, or a group in which they are combined. Examples of the alkyl group having 2 to 20 carbon atoms include an ethyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, an isobutyl group, a tert-butyl group, a 3,3-dimethylbutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, an undecyl group, a dodecyl group, a hexadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. m represents an integer of 1 to 6, and n represents an integer of 1 to 30. When m is 2 or more, n in each group in parentheses in general formula (12) may be the same or different.

[0221] The compound represented by the general formula (12) is, for example, a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0222] The acid value of the compound (E1) having an epoxy group is preferably 10 mgKOH / g or less.

[0223] The compound (E1) having an epoxy group can be used alone or in combination of two or more kinds.

[0224] The content of the compound (E1) having an epoxy group is preferably from 0.5 to 20 mass %, and more preferably from 1 to 15 mass %, in 100 mass % of the thermally crosslinkable compound (E).

[0225] (Compound (E2) Having a Blocked Isocyanate Group) The thermally crosslinkable compound (E) preferably contains a compound (E2) having a blocked isocyanate group.

[0226] The compound (E2) having a blocked isocyanate group is a compound in which the isocyanate group of a compound having an isocyanate group is protected with a blocking agent. The desorption temperature of the blocking agent of the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C, and particularly preferably 80 to 100°C.

[0227] 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, the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, etc.

[0228] 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, mercaptan compounds, imidazole compounds, and imide compounds, more preferably oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds, and particularly preferably active methylene compounds from the viewpoint of resistance after low-temperature heating. The elimination temperature of the active methylene compound or the temperature of the ester exchange reaction is low at 80 to 110°C, and the reaction is sufficient even at low temperatures, improving resistance.

[0229] 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; Compounds having an alicyclic structure, such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane; Examples of the aromatic compounds include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyl diphenylmethane diisocyanate, tetraalkyl diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethyl xylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bischloromethyl diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanate methyl)benzene. Further examples include biuret forms, isocyanurate forms, adduct forms, allophanate forms, and reaction products of these compounds with polyols.

[0230] The compound having an isocyanate group is preferably a biuret, isocyanurate, adduct or allophanate of a compound having an aliphatic structure or a compound having an alicyclic structure.

[0231] Examples of the compound (E2) having a blocked isocyanate group include the following compounds: In the following structural formulas, X represents a blocked isocyanate group, but the present invention is not limited thereto.

[0232] [ka]

[0233] Examples of X (blocked isocyanate group) in the above compound include the structures shown in (X-1) to (X-6) below. In the following structures, * represents a bond. However, the present invention is not limited to these.

[0234] [ka]

[0235] Examples of commercially available compounds (E2) having a blocked isocyanate group and 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, Inc., and BI7960, BI7961, BI7982, BI7991, and BI7992 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an alicyclic structure include Takenate B-846N manufactured by Mitsui Chemicals, Inc., Coronate BI-301, 2507, and 2554 manufactured by Tosoh Corporation, and BI7950, BI7951, and BI7990 manufactured by Baxenden Chemical Co., Ltd.; Examples of compounds having an aromatic structure include Takenate B-830 and B-815N manufactured by Mitsui Chemicals.

[0236] The compound (E2) having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0237] The weight average molecular weight of the compound (E2) having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0238] The acid value of the compound (E2) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0239] The compound (E2) having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0240] The content of the compound (E2) having a blocked isocyanate group is preferably from 0.5 to 20 mass %, more preferably from 1 to 15 mass %, in 100 mass % of the thermally crosslinkable compound (E).

[0241] From the viewpoint of resistance after low-temperature heating, it is more preferable to use the thermally crosslinkable compound (E) in combination with a compound (E1) having an epoxy group and a compound (E2) having a blocked isocyanate group. The mass ratio of the compound (E1) having an epoxy group to the compound (E2) having a blocked isocyanate group is preferably from 5:95 to 95:5, and more preferably from 10:90 to 90:10.

[0242] [Ultraviolet absorber (F)] From the viewpoint of pattern formability, the red photosensitive composition of the present invention preferably contains an ultraviolet absorber (F), which suppresses the influence of changes in exposure dose and the type and amount of polymerization initiator, and provides a stable pattern width.

[0243] The ultraviolet absorbent (F) is not particularly limited, and can use a known compound. For example, benzophenone compound, benzotriazole compound, triazine compound, conjugated diene compound, methyldibenzoyl compound, coumarin compound, acrylonitrile compound, benzothiazole compound, salicylate compound, etc. can be mentioned. Among these, it is preferable to contain benzophenone compound.

[0244] 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 Uvinal A, 3049, 3050, and UVA-935LH manufactured by BASF Japan, and Adeka STAB 1413 manufactured by ADEKA. Among these, 2,2',4,4'-tetrahydroxybenzophenone and 4,4'-bis(diethylamino)benzophenone are preferred.

[0245] Benzotriazole compounds include, for example, 2-(5-tert-butyl-2-hydroxyphenyl)benzotriazole, ester compounds of benzenepropanoic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy (C7-9 side chain and straight chain alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, and 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol. , 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, etc. Commercially available products include, for example, Tinuvin PS, 99-2, 326, 384-2, 900, 928, 970, 1130, UVA-903KT manufactured by BASF Japan, and Adeka STAB LA-31RG, LA-31G, etc. manufactured by ADEKA Corporation.

[0246] Examples of the triazine compound include a reaction product of 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl)-5-hydroxyphenyl with [(C10-C16 (mainly C12-C13) alkyloxy)methyl]oxirane, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4- Examples of the bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, etc. Examples of commercially available products include Tinuvin 400, 405, 406, 477, and 479 manufactured by BASF Japan, and Adeka STAB LA-46 and LA-F70 manufactured by ADEKA.

[0247] An example of the conjugated diene compound is UV503 manufactured by Daito Chemical Co., Ltd.

[0248] Examples of the methyldibenzoyl 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.

[0249] Examples of the coumarin compound include 4-hydroxycoumarin and 7-hydroxycoumarin.

[0250] The ultraviolet absorbents (F) can be used alone or in combination of two or more kinds.

[0251] The content of the ultraviolet absorber (F) is preferably from 0.1 to 5% by mass based on 100% by mass of the nonvolatile content of the red photosensitive composition.

[0252] [Basic pigment derivatives (G)] From the viewpoint of storage stability, the red photosensitive composition of the present invention preferably contains a pigment derivative (G) having basicity. The pigment derivative (G) having basicity is mainly used for the purpose of improving the dispersibility of the colorant (A). This allows the colorant (A) to be stably dispersed. Note that such use of the pigment derivative (G) having basicity is only one example, and it may also be used for other purposes.

[0253] The pigment derivative (G) having basicity is not particularly limited, and a known compound can be used. For example, a compound having a structure in which a part of a compound having a pigment structure is substituted with a basic group can be mentioned.

[0254] Examples of compounds having a pigment structure include diketopyrrolopyrrole compounds, phthalocyanine compounds, anthraquinone compounds, quinacridone compounds, dioxazine compounds, perinone compounds, perylene compounds, thiazineindigo compounds, triazine compounds, benzimidazolone compounds, benzoisoindole 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 these, diketopyrrolopyrrole compounds, anthraquinone compounds, benzoisoindole compounds, isoindoline compounds, and quinophthalone compounds are preferred, and benzoisoindole compounds and quinophthalone compounds are more preferred.

[0255] Examples of the basic group include an amino group, a pyridinyl group and its salts, an ammonium group salt, etc. Examples of compounds that form salts include a hydroxide ion, a halogen ion, a carboxylate ion, a sulfonate ion, etc.

[0256] The timing of adding the pigment derivative (G) having basicity is preferably when the colorant (A) is micronized or when the colorant (A) is dispersed. The average primary particle size of the pigment derivative (G) having basicity is preferably 5 to 200 nm.

[0257] The pigment derivative (G) having basicity can be used alone or in combination of two or more kinds.

[0258] The content of the basic pigment derivative (G) is preferably from 1 to 50 parts by mass, and more preferably from 2 to 40 parts by mass, based on 100 parts by mass of the colorant (A).

[0259] The pigment derivative (G) having basicity is preferably a compound represented by the following general formula (13) or a compound represented by the following general formula (14), and it is more preferable to use these in combination.

[0260] General formula (13) [ka]

[0261] In the general formula (13), R1 represents a group represented by the following general formula (15).

[0262] In the general formula (13), R2 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group.

[0263] In 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 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms).

[0264] General formula (15) [ka]

[0265] In general formula (15), X represents a single bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC6H4CO-, or -CONHC6H4-.

[0266] In 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 together form a heterocycle. The alkyl group having 1 to 20 carbon atoms may be any of linear, branched, and cyclic alkyl groups, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, and a cyclohexylmethyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. The aryl group may be a group substituted with a halogen atom, an amino group, a nitro group, etc.

[0267] In the general formula (15), n represents an integer of 0 to 20.

[0268] General formula (14) [ka]

[0269] In general formula (14), R8 represents a group represented by general formula (16).

[0270] In general formula (14), R9~R 12 each independently represents a hydrogen atom or a halogen atom.

[0271] General formula (16) [ka]

[0272] In the general formula (16), Y1 is a single bond, -NR 14 SO2-, -SO2NR 14 -,-CONR 14 -, -NR 14 CO- or -CHNR 14 COCH2NR 14 - represents. R 14 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 30 carbon atoms.

[0273] In the general formula (16), Y2 represents a single bond, an arylene group, or an aromatic ring, and these are represented by -NR 14 They may be bonded to each other via a divalent linking group selected from -, -O-, -SO2-, or -CO-.

[0274] In the general formula (16), Y3 is a single bond, -NR 14 It represents - or -O-.

[0275] In general formula (16), R 13 represents a group represented by general formula (15).

[0276] Specific examples of the compound represented by formula (13) are shown below, but the present invention is not limited to these.

[0277] [ka]

[0278] Specific examples of the compound represented by formula (14) are shown below, but the present invention is not limited to these.

[0279] [ka]

[0280] When the compound represented by general formula (13) and the compound represented by general formula (14) are used in combination, the mass ratio of the compound represented by general formula (13) to the compound represented by general formula (14) is preferably 95:5 to 5:95, and more preferably 95:5 to 50:50.

[0281] The method for producing the compound represented by the general formula (13) and the compound represented by the general formula (14) is not particularly limited, and a known method can be used, for example, the methods described in JP-A-2006-291194 and JP-A-2008-069343.

[0282] [Thiol-based chain transfer agents (H)] The red-sensitive composition of the present invention may contain a thiol-based chain transfer agent (H).

[0283] Examples of the thiol-based chain transfer agent (H) include monofunctional thiol 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, and 2-ethylhexyl 3-mercaptopropionate; Monofunctional thiol compounds having a hydroxyl group or an acidic group, such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, and 2-mercaptoethanesulfonic acid; Examples of polyfunctional thiol compounds include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0284] The thiol chain transfer agent (H) can be used alone or in combination of two or more kinds.

[0285] The content of the thiol chain transfer agent (H) is preferably from 0.5 to 10% by mass based on 100% by mass of the nonvolatile content of the red photosensitive composition.

[0286] [Silane coupling agents (I)] The red photosensitive composition of the present invention may contain a silane coupling agent (I).

[0287] The silane coupling agent (I) is a compound having a hydrolyzable group and other functional groups. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of hydrolysis and condensation reactions. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. Examples of the other 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 oxetanyl group, a styryl group, and a ureido group. In this specification, the silane coupling agent (I) is not included in the resin (B) having an acidic group and the polymerizable compound (C).

[0288] 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, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane. hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, and the like.

[0289] Commercially available silane coupling agents (I) include, for example, 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, and KBE -1003, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBE-585A, X-12-1048, X-12-50, etc.

[0290] The silane coupling agent (I) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0291] The polysiloxane type is a compound in which the hydrolyzable group and the other functional groups are bonded to a polymer having a polysiloxane skeleton in the main chain. Commercially available polysiloxane type products include KR-513, KR-516, KR-517, X-41-1805, and X-41-1810 manufactured by Shin-Etsu Silicone Co., Ltd.

[0292] The organic polymer type is a silane coupling agent (I) in which the hydrolyzable group and the other functional groups are bonded to an organic polymer whose main chain is an organic structure. Commercially available organic polymer type products include X-12-9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, etc., manufactured by Shin-Etsu Silicone Co., Ltd.

[0293] The silane coupling agent (I) preferably contains a compound represented by the following general formula (17). The compound represented by general formula (17) has a urethane bond, and therefore forms hydrogen bonds between the urethane bonds and with functional groups of other components contained in the photosensitive composition, forming a strong film. In addition, it is presumed that the urethane bond has flexibility, resulting in a strong yet flexible film.

[0294] General formula (17) [ka]

[0295] In general formula (17), three R1 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 represents a group represented by any one of the following general formulae (Q-1) to (Q-4), and n represents an integer of 1 to 10.

[0296] [ka]

[0297] In the general formula (Q-1), R3 represents an alkylene group having 1 to 8 carbon atoms. In the general formulae (Q-1) to (Q-4), R4 each independently represents a hydrogen atom or a methyl group. * represents a bond to an oxygen atom.

[0298] In the general formula (17), the three R1's are preferably methyl groups.

[0299] In the general formula (17), Q is preferably any of the general formulae (Q-1) to (Q-3).

[0300] The molecular weight (formula weight) or weight average molecular weight of the silane coupling agent (I) is preferably from 100 to 3,000, and more preferably from 150 to 1,500.

[0301] The acid value of the silane coupling agent (I) is preferably 10 mgKOH / g or less.

[0302] The silane coupling agent (I) can be used alone or in combination of two or more kinds.

[0303] The content of the silane coupling agent (I) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the red photosensitive composition.

[0304] [Leveling agent (J)] The red photosensitive composition of the present invention may contain a leveling agent (J), which improves the wettability and drying property of the composition to a substrate during application.

[0305] Examples of the leveling agent (J) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0306] Examples of silicone surfactants include linear polymers formed from siloxane bonds, modified siloxane polymers in which organic groups have been introduced into the side chains or ends, and polymers having a siloxane structure in the side chain.

[0307] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 2110 manufactured by Dow Corning Toray Co., Ltd. , 2122, 2123, 2191, 5609, and Shin-Etsu Silicones' 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, and KP-341. Further examples include polymers described in WO 2019 / 078080, WO 2021 / 131726, WO 2022 / 050062, WO 2022 / 059492, WO 2022 / 130990, and WO 2022 / 244586.

[0308] The fluorosurfactant may be, for example, a surfactant or a leveling agent having a fluorocarbon chain.

[0309] 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, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

[0310] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, and alkyl imidazolines.

[0311] Commercially available products include, for example, 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, manufactured by Kao Corporation. LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMURU PD-420, PD-430, PD-430S, PD-450, Leodor 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, T W-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, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Ami-to 10 2, 105, 105A, 302, 320, Aminone 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 Corporation, and (meth)acrylic acid copolymer Polyflour No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0312] Examples of the cationic surfactant include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0313] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0314] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0315] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0316] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethyl amino acetate betaine; and alkyl amine oxides such as lauryl dimethyl amine oxide.

[0317] Commercially available products include Anhythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0318] The leveling agent (J) can be used alone or in combination of two or more kinds.

[0319] The content of the leveling agent (J) is preferably from 0.001 to 2.0% by mass in 100% by mass of the nonvolatile content of the red photosensitive composition. [Organic solvent (K)] The red-sensitive composition of the present invention may contain an organic solvent (K).

[0320] The organic solvent (K) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methanol ... 1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, 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 monotertiary 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.,

[0321] From the viewpoint of storage stability, the organic solvent (K) preferably contains an organic solvent having a hydroxyl group.Specific examples thereof include 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, and 2-methyl-1,3-propanediol. From the viewpoint of storage stability, the content of the organic solvent having a hydroxyl group is preferably from 0.1 to 20% by mass in 100% by mass of the organic solvent (K).

[0322] The organic solvent (K) can be used alone or in combination of two or more kinds.

[0323] The content of the organic solvent (K) is preferably such that the non-volatile content of the red photosensitive composition is 5 to 60% by mass.

[0324] [Other components (L)] The red photosensitive composition of the present invention may contain components other than those described above (hereinafter, also referred to as other components (L)). Examples of the other components (L) include resins that do not have an acidic group (e.g., resins that have a basic group), pigment derivatives that do not have a basic group (e.g., pigment derivatives that have an acidic group), polymerization inhibitors, antioxidants, sensitizers, acid generators, salt generators, curing accelerators, curing catalysts, near-infrared absorbers, semiconductor nanocrystals, semiconductor materials, organic electroluminescent materials, and insulating materials. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0325] [Specific metal element content] The red photosensitive composition of the present invention preferably has a total content of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) of 500 mass ppm or less.

[0326] A red photosensitive composition in which the total amount of the specific metal elements is within the above range has excellent dispersion stability and sensitivity even after storage over time. The content of the specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0327] [Water content] The red photosensitive composition of the present invention preferably contains water in an amount of 2.0% by mass or less.

[0328] A red photosensitive composition having a water content within the above range has excellent dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0329] [Method for producing red-sensitive composition] The red-sensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the composition, the components may be mixed at once, or each component may be dissolved or dispersed in the polymerizable compound (C) or the organic solvent (K) and then mixed successively. For example, a dispersion is produced by adding a color material (A), a resin (B) having an acidic group, an organic solvent (K), and the like, and carrying out a dispersion treatment. Then, a polymerizable compound (C), a polymerization initiator (D), and the like are compounded and mixed with the dispersion to produce the dispersion. The timing for compounding each material is arbitrary. The dispersion process can also be carried out multiple times.

[0330] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0331] The average dispersed particle size (secondary particle size) of the particles in the dispersion is preferably from 30 to 200 nm, more preferably from 40 to 200 nm. If the particles have an appropriate particle size, a red photosensitive composition having high dispersion stability is easily obtained.

[0332] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to give results with less variation.

[0333] The red-sensitive composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The red-sensitive 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.

[0334] The red photosensitive composition of the present invention is preferably used for forming a pattern by a photolithography method, although the present invention is not limited thereto.

[0335] <Membrane> The film of the present invention is a film formed from the above-mentioned red-sensitive composition. The film is preferably a patterned film, but may also be used as a flat film without forming a pattern.

[0336] [Membrane manufacturing method] The method for producing the film is not particularly limited, and known methods can be used. In the production of the film in the present invention, the heating temperature throughout the entire process is preferably 150°C or less, more preferably 130°C or less, from the viewpoint of the environment. In addition, by carrying out heating at 150°C or less, when an organic EL element is used as the light emitting source of the image display device, when the photoelectric conversion film of the image sensor is made of an organic material, when a heat-sensitive base material such as a plastic film is used, and the like, can be maintained. In addition, the heating temperature is preferably 50°C or more.

[0337] In the production of the film, first, the red photosensitive composition is applied onto a substrate. Examples of the substrate include glass, resin, silicon, and the like. The glass is preferably colorless and transparent. Depending on the application, colored glass such as blue glass may be used. The substrate may have an organic light-emitting layer. The substrate may also have an imaging element such as a CCD or CMOS. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0338] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0339] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0340] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. Among these, a photolithography method is preferable. When the film is used as a flat film, the step of forming a pattern is not necessary, and after coating, the film is dried or the entire surface is exposed to light as necessary.

[0341] A method for forming a pattern by photolithography will be described in detail below. In the photolithography method, a layer formed by coating the red photosensitive composition of the present invention on a substrate is dried at a temperature of 150°C or less as necessary, and then exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed by alkaline development (development step), and the pattern is then heat-treated (heating step).

[0342] [Exposure process] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure). In addition, a plurality of active energy rays may be used in combination, or exposure may be performed in a plurality of steps.

[0343] [Development process] Next, the layer is treated with an alkaline developer, whereby the unexposed portions are dissolved in the alkaline developer, leaving only the hardened portions to obtain a patterned film. Examples of alkaline developers 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. 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 used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0344] [Heating process] After development, a heat treatment is performed, which improves the resistance of the film. The heating temperature is preferably equal to or lower than 150° C., more preferably equal to or lower than 130° C. The heating time is preferably about 2 minutes to 2 hours.

[0345] <Color filters> 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.

[0346] <Solid-state imaging element> The solid-state imaging device of the present invention has the above-mentioned color filter. The solid-state imaging device is not particularly limited as long as it has the color filter of the present invention and functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0347] The substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film with only the light receiving portion of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and a color filter of the present invention on the device protection film. Furthermore, the device protection film may have a light collecting means (e.g., a microlens, etc., the same below) on the device protection film and below the color filter (on the side closer to the substrate), or a light collecting means on the optical filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned by partitions, for example, in a lattice shape. In this case, the partitions preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, and surveillance cameras.

[0348] <Image display device> The image display device of the present invention has the above-mentioned color filter. Examples of the image display device include a liquid crystal display and an organic EL display. The form of 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 given.

[0349] The liquid crystal display includes a color filter, a counter substrate having a TFT array substrate or the like, and a liquid crystal layer formed between the color filter and the counter substrate. Examples of driving methods for liquid crystal displays include the TN method, the IPS method, the OCB method, and the MVA method. The counter substrate can be appropriately selected according to the driving method. The liquid crystal layer can use various liquid crystals with different dielectric anisotropy and mixtures thereof according to the driving method.

[0350] Specifically, it is described in "Next Generation Liquid Crystal Display Technology" (by Uchida Tatsuo, published by Kogyo Chosakai Co., Ltd. in 1994), "Electronic Display Devices" (by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989). EXAMPLES

[0351] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 110°C for 3 hours.

[0352] Before describing the examples, each measurement method will be described.

[0353] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and absorption coefficient (L / mol cm) of the resin are measured as follows.

[0354] (Molecular weight) Number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0355] (Acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of sample solution, and the solution was stirred to dissolve uniformly. The solution was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) was measured. The acid value per unit of nonvolatile content was calculated from the acid value of the solution and the concentration of nonvolatile content in the solution.

[0356] (Extinction coefficient) 0.001 g of polymerization initiator was dissolved in 0.01 L of propylene glycol monomethyl ether acetate to prepare a 0.1 mass% measurement solution. The 0.1 mass% measurement solution was then diluted with propylene glycol monomethyl ether acetate to prepare 0.01 mass% and 0.001 mass% measurement solutions. The absorbance of each concentration of the measurement solution was measured at a wavelength of 365 nm using a spectrophotometer (Hitachi High-Technologies Corporation, "U-3010"), and the extinction coefficient (L / mol cm) was calculated from the slope when the horizontal axis was the molar concentration and the vertical axis was the absorbance.

[0357] <Production of Colorant (A)> (Purple color material (A4-1)) A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight was 6,830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50° C. for 2 hours, then heated to 80° C. over 1 hour, and reacted for 2 hours to obtain Resin 1. Next, 30 parts of resin 1 in terms of non-volatile content was added to 2,000 parts of water, and after thorough stirring and mixing, it was heated to 60 ° C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52, a compound having a xanthene skeleton, in 90 parts of water, and was dropped little by little into the resin 1 solution. After dropping, it was stirred at 60 ° C for 120 minutes and reacted thoroughly. To confirm the end point of the reaction, the reaction liquid was dropped onto a filter paper, and the end point was determined to be when the bleeding disappeared, and it was determined that a salt-forming compound was obtained. After cooling to room temperature while stirring, it was filtered by suction, washed with water, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain a purple colorant (A4-1), which is a salt-forming 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 colorant (A4-1) was 25 mass%.

[0358] (Purple color material (A4-2)) A purple colorant (A4-2) was produced in the same manner as for the purple colorant (A4-1), except that CI Acid Red 52 was changed to CI Acid Red 289. At this time, the content of the component derived from CI Acid Red 289 in the purple colorant (A4-2) was 25% by mass.

[0359] (Purple color material (A4-3)) A reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 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-methacryloxymethyloxetane, and 15.0 parts of tert-butyl methacrylate, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was replaced 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 charged, and the temperature was raised to 100°C under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as the second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining the temperature at 100°C under a nitrogen atmosphere. Two hours after adding the dimethylaminoethyl methacrylate methyl chloride salt, a sample of the polymerization solution was taken and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile content, and after cooling to 50°C, methanol was added to obtain resin 2. The weight average molecular weight was 7,700. Next, 30 parts of resin 2 in terms of non-volatile content was added to 2,000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of a compound represented by the following chemical formula (18) in 90 parts of water, and the solution was gradually dropped into the previous resin 2 solution. After dropping, the solution was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain a purple colorant (A4-3) which is a salt-forming compound of 32 parts of the compound represented by chemical formula (18) and resin 2. At this time, the content of the component derived from the compound represented by chemical formula (18) in the purple colorant (A4-3) was 25% by mass.

[0360] Chemical formula (18) [ka]

[0361] (Purple color material (A4-4)) The following purple colorant (A4-4) was synthesized according to paragraphs 0102 to 0104 of JP 2015-57487 A. The numerical values ​​shown next to the repeating units are mass ratios.

[0362] [ka]

[0363] <Production of Resin (B) Having Acidic Groups> (Resin (B1-1) solution having aromatic carboxyl group) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, calculated as non-volatile content, 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 methyl acrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were charged, and the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the reaction was carried out for 12 hours (second step). It was confirmed that 95% had reacted by measuring the non-volatile content. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR showed that 2,270 cm3 based on the isocyanate group was obtained. -1The reaction was continued until the disappearance of the peak was confirmed (third step). After cooling, PGMAc was added so that the non-volatile content was 30 mass%, to prepare a resin (B1-1) solution having an aromatic carboxyl group. The molar ratio of pyromellitic dianhydride / 3-mercapto-1,2-propanediol was 0.8, the acid value was 68 mgKOH / g, and the weight average molecular weight was 13,000.

[0364] (Resin (B1-2) solution having aromatic carboxyl group) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 20.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, 5.0 parts of methacrylic acid, and 25.0 parts of PGMAc, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution in which 0.1 parts of 2,2'-azobisisobutyronitrile was dissolved in 45.7 parts of PGMAc was added, and the reaction was carried out for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride, 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 reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-2) solution having an aromatic carboxyl group was prepared. The pyromellitic dianhydride / 3-mercapto-1,2-propanediol ratio was 1.2 (molar ratio), the acid value was 105 mg KOH / g, and the weight average molecular weight was 9,500.

[0365] (Resin (B1-3) solution having aromatic carboxyl group) A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 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, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 10 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, and a resin (B1-3) solution having aromatic carboxyl groups was prepared. The molar ratio of pyromellitic dianhydride / 3-mercapto-1,2-propanediol was 0.78, the acid value was 70 mgKOH / g, and the weight average molecular weight was 8,500.

[0366] (Resin (B2-1) solution not having aromatic carboxyl group) According to WO 2016 / 103994, a solution of the following copolymer resin (B2-1) not having an aromatic carboxyl group was prepared by adding PGMAc so that the non-volatile content was 30% by mass. The acid value was 51.7 mg KOH / g and the weight average molecular weight was 13,000. The value written next to the repeating unit of the main chain is the molar ratio, and the value written next to the repeating unit of the side chain is the number of repeating parts.

[0367] [ka]

[0368] (Resin (B2-2) solution not having aromatic carboxyl group) According to WO 2016 / 103994, a solution of the following copolymer resin (B2-2) without aromatic carboxyl groups was prepared by adding PGMAc so that the non-volatile content was 30% by mass. The acid value was 58.2 mg KOH / g and the weight average molecular weight was 10,000. The value written next to the repeating unit of the main chain is the molar ratio, and the value written next to the repeating unit of the side chain is the number of repeating parts.

[0369] [ka]

[0370] (Resin (B2-3) solution not having aromatic carboxyl group) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether, which was then stirred while replacing with nitrogen and heated to 78°C. Next, a mixture of 25.2 parts of Karenz MOI-DEM (2-methyl-1-oxo-2-propenyl)oxy]ethyl]amino]carbonyl]-1,3-diethyl ester of malonic acid 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 12.0 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) dissolved in 50 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 78°C for 3 hours to react. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-3) having no aromatic carboxyl group. The acid value was 74 mgKOH / g, and the weight average molecular weight was 8,000.

[0371] (Resin (B2-4) solution not having aromatic carboxyl group) In a four-neck flask equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 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 and stirred, and cooled to 15 to 20°C. Then, while maintaining the temperature at 15 to 20°C and stirring, 141.1 parts of 2-acryloyloxyethyl isocyanate were dropped from the dropping funnel. After the dropwise addition, the mixture was stirred and reacted at 25°C for 13 hours to obtain compound a. Next, 150 parts of propylene glycol monomethyl ether was put into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and then the mixture was stirred while replacing with nitrogen and heated to 78 ° C. 148.8 parts of compound a, Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate manufactured by Showa Denko K.K.) 24.7 parts, 2-hydroxyethyl methacrylate 25.5 parts, 2-ethylhexyl acrylate 8.6 parts, and 17.4 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) (polymerization initiator) were mixed and dropped into the flask from the dropping funnel. After the dropwise addition, 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 further stirred at 78 ° C for 30 minutes. 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. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-4) having no aromatic carboxyl group. The acid value was 44 mgKOH / g, and the weight average molecular weight was 12,500.

[0372] (Resin (B2-5) solution not having aromatic carboxyl group) 100 parts of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and then the mixture was stirred while replacing with nitrogen and heated to 90°C. Next, a mixture of 20.7 parts of 2-(acetoacetoxy)ethyl methacrylate, 26.7 parts of methacrylic acid and 52.6 parts of dicyclopentanyl methacrylate, and 5.0 parts of 2,2'-azobis(isobutyric acid)dimethyl dissolved in 30 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was stirred at 90°C for 6 hours to react. The mixture was then cooled to 40°C, and 0.12 parts of 4-methoxyphenol, 17.6 parts of 3,4-epoxycyclohexylmethyl acrylate, and 4.7 parts of triphenylphosphine were added, and the temperature was raised to 110°C, followed by stirring for 10 hours to carry out the reaction. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-5) having no aromatic carboxyl group. The acid value was 103 mgKOH / g, and the weight average molecular weight was 14,300.

[0373] (Resin (B2-6) solution not having aromatic carboxyl group) 200 parts of 3-methoxy-1-butanol was added to a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube, and the mixture was stirred while replacing with nitrogen and heated to 105°C. Next, a mixture of 106.9 parts of 3-methacryloyloxypropyltrimethoxysilane, 40.8 parts of methacrylic acid and 125 parts of methyl methacrylate, and 27.3 parts of dimethyl 2,2'-azobis(isobutyrate) was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was reacted for 2 hours while stirring at 105°C. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, and a solution of a resin (B2-6) having no aromatic carboxyl group was prepared. The acid value was 99 mgKOH / g, and the weight average molecular weight was 7,100.

[0374] (Resin (B2-7) solution not having aromatic carboxyl groups) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of propylene glycol monomethyl ether, which was then stirred while replacing with nitrogen and heated to 90°C. 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 t-butylperoxy-2-ethylhexanoate (polymerization initiator) and a mixture of 0.6 parts of n-dodecyl mercaptan and 20 parts of PGMAc were dropped into the flask from the dropping funnel. After the dropwise addition, the mixture was kept at 90°C for 30 minutes, then heated to 115°C and reacted with stirring for 90 minutes. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-7) having no aromatic carboxyl group. The acid value was 98 mgKOH / g, and the weight average molecular weight was 19,500.

[0375] (Resin (B2-8) solution not having aromatic carboxyl groups) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer to form a reaction vessel. 200 parts of propylene glycol monomethyl ether was placed in the vessel, and heated to 120°C while injecting nitrogen gas into the vessel. 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 was added dropwise from the dropping tube over 2.5 hours, and a polymerization initiator was dissolved in 5.0 parts of azobisisobutyronitrile PGMAc to carry out the polymerization reaction. After the dropwise addition, the mixture was stirred at 120°C for another 2 hours to carry out the reaction. Next, the flask was substituted with air, and 28.82 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the mixture was stirred at 120°C for 5 hours to carry out the reaction. Further, 32.0 parts of succinic anhydride and 0.5 parts of triethylamine were added, and the mixture was reacted at 120° C. for 4 hours with stirring. Thereafter, PGMAc was added so that the non-volatile content became 30% by mass, to prepare a solution of a resin (B2-8) having no aromatic carboxyl group. The resin had an acid value of 77 mgKOH / g and a weight average molecular weight of 10,000.

[0376] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, and then dispersed in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The non-volatile content was 21.0 mass%. Red color material (A1-1): 15.0 parts Resin (B1-1) solution having aromatic carboxyl group: 15.0 parts Pigment derivative having a basic group (G-1): 1.5 parts Organic solvent (K-1): 68.5 parts

[0377] (Dispersion 2~18) Dispersions 2 to 18 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts thereof were changed as shown in Tables 1-1 and 1-2.

[0378] [Table 1-1]

[0379] [Table 1-2]

[0380] The components listed in Tables 1-1 and 1-2 are as follows.

[0381] Colorant (Red color material (A1)) A1-1: CI Pigment Red 264 A1-2: CI Pigment Red 179 A1-3: CI Pigment Red 177

[0382] (Yellow color material (A2)) A2-1: CI Pigment Yellow 139 A2-2: CI Pigment Yellow 185

[0383] (Blue color material (A3)) A3-1: CI Pigment Blue 15:6

[0384] The red color material (A1), the yellow color material (A2), and the blue color material (A3) were all finely milled by salt milling, thoroughly washed with ion-exchanged water so as to have the specific metal contents described above, and then dried before use.

[0385] [Pigment derivatives (G)] [ka]

[0386] [Organic solvent (K)] K-1:PGMAc

[0387] [Other components (L)] L-1: LP-N21116 (manufactured by BYK-Chemie, resin with basic groups) L-2: Compound having the following structure (pigment derivative having an acidic group)

[0388] [ka]

[0389] <Production of Red-Sensitive Composition> [Example 1] (Red photosensitive composition 1) 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 non-volatile content was 15.0 mass%. In Table 2-1, Dispersions 1 and 2 are decomposed into their constituent components, and the organic solvent (K-1) of the dispersion is included in the organic solvent (K). Dispersion 1: 22.50 parts Dispersion 8: 2.50 parts Resin solution without aromatic carboxyl group (B2-3): 6.30 parts Resin solution without aromatic carboxyl group (B2-8): 6.30 parts Polymerizable compound having an amine structure (C1-1): 0.75 parts Polymerizable compound having a hydroxyl group (C2-1): 2.20 parts Polymerizable compound having a dendrimer structure or a hyperbranched structure (C3-1): 0.50 parts Polymerization initiator (D1-1): 0.10 parts Polymerization initiator (D1-3): 0.10 parts Compound having an epoxy group (E1-1): 0.45 parts Compound having a blocked isocyanate group (E2-1): 1.75 parts UV absorber (F-1): 0.30 parts Thiol chain transfer agent (H): 0.20 parts Silane coupling agent (I): 0.30 parts Leveling agent (J): 0.02 parts Organic solvent (K): 55.73 parts

[0390] [Examples 2 to 43 and Comparative Example 1] (Red photosensitive composition 2-44) Red photosensitive compositions 2 to 44 were produced in the same manner as in Example 1 using the raw materials and amounts shown in Tables 2-1 to 2 to 5. In Tables 2-1 to 2 to 5, dispersions 1 to 18 are broken down into their constituent components and shown, and the organic solvent (K-1) of the dispersion is shown as being included in the organic solvent (K).

[0391] [Table 2-1]

[0392] [Table 2-2]

[0393] [Table 2-3]

[0394] [Table 2-4]

[0395] [Table 2-5]

[0396] The respective raw materials listed in Tables 2-1 to 2-5 are as follows.

[0397] [Polymerizable compound (C)] (Polymerizable compound (C1) having an amine structure) C1-1: CN9906 (Arkema, multifunctional acrylate with an amine structure) C1-2: Aronix MT-3041 (manufactured by Toagosei Co., Ltd., a multifunctional acrylate having an amine structure)

[0398] (Polymerizable compound having a hydroxyl group (C2)) C2-1: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) C2-2: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[0399] (Polymerizable compound (C3) having a dendrimer structure or a hyperbranched structure) C3-1: Miramer SP-1106 (Miwon Specialty Chemical Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups) C3-2: SIRIUS-501 (Osaka Organic Chemical Industry Co., Ltd., a compound having a dendrimer structure with an average number of 18 acryloyl groups, non-volatile content 50% by mass)

[0400] (Other polymerizable compounds (C7)) C7-1: KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol EO modified hexaacrylate)

[0401] [Polymerization initiator (D)] (Polymerization initiator (D1)) D1-1: The above compound (D1-1) (absorption coefficient of light with a wavelength of 365 nm is 18,334 L / mol cm) D1-2: The above compound (D1-2) (absorption coefficient of light with a wavelength of 365 nm is 27,257 L / mol cm) D1-3: The above compound (D1-3) (absorption coefficient of light with a wavelength of 365 nm is 13,410 L / mol cm) D1-4: The above compound (D1-4) (absorption coefficient of light with a wavelength of 365 nm is 14,214 L / mol cm) D1-5: The above compound (D1-5) (absorption coefficient of light with a wavelength of 365 nm is 18,767 L / mol cm) D1-6: The above compound (D1-6) (absorption coefficient of light with a wavelength of 365 nm is 7,051 L / mol cm)

[0402] (Polymerization initiator (D2) other than polymerization initiator (D1)) D2-1: Irgacure OXE-02 (absorption coefficient of light at a wavelength of 365 nm is 2,401 L / mol cm)

[0403] [Thermal crosslinkable compound (E)] (Compound (E1) having an epoxy group) E1-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (12), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0404] (Compound (E2) Having a Blocked Isocyanate Group) E2-1: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, a compound blocked with an active methylene compound, non-volatile content 60% by mass)

[0405] [Ultraviolet absorber (F)] F-1: A mixture of 4,4'-bis(diethylamino)benzophenone and 2,2',4,4'-tetrahydroxybenzophenone in a mass ratio of 5:5 F-2: A compound having the following structure

[0406] [ka]

[0407] [Thiol chain transfer (H)] A mixture of mercaptosuccinic acid and pentaerythritol tetrakis(3-mercaptopropionate) in a mass ratio of 5:5

[0408] [Silane coupling agents (I)] X-12-1048 (Shin-Etsu Silicones Co., Ltd., a compound represented by general formula (17)

[0409] [Leveling agent (J)] A mixture of BYK-330 (manufactured by BYK-Chemie, polyether-modified dimethylsiloxane) and a block copolymer (n:m = 50:50 (mol%)) having the following structure in a mass ratio of 8:2

[0410] [ka]

[0411] [Organic solvent (K)] K-1:PGMAc K-2: Cyclohexanone K-3: Ethyl 3-ethoxypropionate The above K-1, K-2, and K-3 were mixed in a mass ratio of 8:1:1 to prepare an organic solvent (K).

[0412] <Evaluation of Red-sensitive Composition> The following evaluations were carried out on the obtained red photosensitive compositions 1 to 44. The evaluation results are shown in Table 3.

[0413] [Storage stability evaluation (1): Foreign matter] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. After cooling to room temperature, the composition was exposed to light using an ultra-high pressure mercury lamp with an illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 A cured film was prepared by exposure to light at 400 nm. The number of foreign matters on the prepared cured film was counted, and all of the obtained red photosensitive compositions had less than 10. This was taken as the initial number of foreign matters. The measurement was performed using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.) at a magnification of 500 times, and the number of foreign matters observable in any five visual fields in transmission was counted by integrating them. The red photosensitive composition was placed in a sealed container and stored at 40° C. for 10 days. The number of foreign matters after storage was counted under the same conditions as in the initial evaluation, and the composition was evaluated according to the following criteria: 3 or more is usable. 5: The number of foreign objects after storage is less than 110% of the initial number of foreign objects. 4: The number of foreign objects after storage is between 110% and 120% of the initial number of foreign objects. 3: The number of foreign objects after storage is between 120% and 140% of the initial number of foreign objects. 2: The number of foreign objects after storage is between 140% and 150% of the initial number of foreign objects. 1: The number of foreign objects after storage is 150% or more of the initial number of foreign objects

[0414] [Storage stability evaluation (2): Film thickness] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. After cooling to room temperature, the composition was exposed to light using an ultra-high pressure mercury lamp through a photomask with a 100 μm wide stripe pattern, with an illumination intensity of 30 mW / cm.2 , 100mJ / cm 2 After cooling the substrate to room temperature, it was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C, washed with ion-exchanged water, and air-dried. The substrate thus obtained was heated in a clean oven at 90°C for 60 minutes, after which the film thickness of the pattern was measured. This film thickness was taken as the initial film thickness. The red photosensitive composition is placed in a sealed container and stored at 40° C. for 10 days. The film thickness after storage is measured under the same conditions as the initial film thickness, and this film thickness is regarded as the film thickness after storage. The film thickness change rate was calculated from the two film thicknesses using the following formula. The evaluation criteria are as follows, with 3 or more being practical. The film thickness is the average value of measurements taken at 10 random locations using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.). Formula: Rate of change (%) = |film thickness after storage - initial film thickness| / initial film thickness x 100 5: The rate of change is less than 3% 4: The rate of change is between 3% and 6%. 3: The rate of change is between 6% and 10%. 2: The rate of change is between 10% and 15%. 1: The rate of change is 15% or more

[0415] [Developability evaluation] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / cm 2 The substrate was exposed to light at 1000 K. After cooling 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-exchanged water, and air-dried. The substrate was observed under an optical microscope to confirm the presence or absence of residues in the unexposed areas. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: When developed in the shortest time possible for pattern formation, no residue was left in the unexposed areas. 4: No residue was left in the unexposed areas after development for 5 seconds longer than the shortest time possible for pattern formation. 3: No residue was left in the unexposed areas after development for 10 seconds longer than the shortest time possible for pattern formation. 2: No residue was left in the unexposed areas after development for 15 seconds longer than the shortest time possible for pattern formation. 1: Residue remained in the unexposed areas even after development for 20 seconds longer than the shortest time possible for pattern formation.

[0416] [Pattern Formation Evaluation (1): Line Width] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm. 2 , exposure dose 50mJ / cm 2 and 100 mJ / cm 2 The substrate was exposed to light through a photomask with a 100 μm wide stripe pattern at two levels. After cooling to room temperature, the substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23° C., washed with ion-exchanged water, and air-dried. The obtained substrate was heated at 90° C. for 60 minutes in a clean oven to obtain a substrate for evaluation. The spray development was performed for each red photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained evaluation substrate was subjected to an exposure of 50 mJ / cm using a Nikon ECLIPSE LV100POL Model optical microscope. 2 Line width (CD 50 ) and 100 mJ / cm 2 Line width (CD 100 The difference in line width (ΔCD) due to the difference in exposure dose was calculated using the following formula (1). The evaluation criteria are as follows, with a score of 3 or higher being considered practical. Equation (1): ΔCD = CD 100 -CD 50 5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6μm or more

[0417] [Pattern Formation Evaluation (2): Linearity] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / cm 2 The substrate was exposed to light at 1000 K. After cooling to room temperature, the substrate 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 substrate was heated in a clean oven at 90° C. for 60 minutes to obtain an evaluation substrate. The spray development was performed for each red photosensitive composition for the shortest time possible to form a pattern without leaving any residual development. The obtained substrate was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with 3 or more being practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0418] [High temperature and humidity resistance evaluation] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Then, after cooling the substrate to room temperature, the substrate was irradiated with an ultra-high pressure mercury lamp at an illumination intensity of 30 mW / cm. 2 , 100mJ / cm 2 After cooling the substrate 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-exchanged 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. The obtained substrate was stored for 200 hours under conditions of a temperature of 85°C and a humidity of 85%. After storage, the film was cut with a cutter knife to create a lattice pattern of 1 mm squares (total of 100 squares), and a transparent adhesive tape (CT-24 manufactured by Nichiban Co., Ltd.) was firmly pressed against the film and peeled off in a direction of about 180 degrees. The state of the lattice patterns was observed, and the number of peeled lattice patterns was counted. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Less than 2. 4: 2 or more but less than 5. 3: 5 or more but less than 10. 2: 10 or more but less than 15. 1:15 or more.

[0419] [Solvent resistance evaluation] The obtained red photosensitive composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the film thickness after drying would be 2.5 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, the substrate was irradiated with light at an illumination intensity of 30 mW / cm using an ultra-high pressure mercury lamp through a photomask with a 100 μm-wide stripe pattern. 2 , 100mJ / cm 2After cooling the substrate 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-exchanged water, and air-dried. The obtained substrate was heated in a clean oven at 90°C for 60 minutes to obtain a substrate for evaluation. The obtained evaluation substrate was immersed in PGMAc at room temperature for 15 minutes, washed with ion-exchanged water, air-dried, and the stripe pattern portion with a width of 100 μm was observed using an optical microscope. The evaluation criteria are as follows, with 3 or more being considered practical. 5: No change in appearance or color. 4: Slight wrinkles etc. occur, but there is no change in color. 3: Some wrinkles or other imperfections occur, but there is no change in color. 2: Wrinkles and other imperfections appear all over the surface, and the color fades slightly. 1: Peeling or fading occurs.

[0420] [Table 3]

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), The color material (A) contains a red color material (A1) and a yellow color material (A2), The red colorant (A1) contains one or more selected from the group consisting of C.I. Pigment Red 179 and C.I. Pigment Red 264, The yellow colorant (A2) contains an isoindoline pigment, The polymerization initiator (D) has an absorption coefficient of 5.0×10 at 365 nm in propylene glycol monomethyl ether acetate. ３ A red photosensitive composition comprising a polymerization initiator (D1) having a viscosity of 1000 sq. m / mol.cm or more.

2. 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.

3. The red-sensitive composition according to claim 1 , wherein the polymerization initiator (D1) comprises a compound having two oxime ester groups.

4. The red-sensitive composition according to claim 1 , further comprising a thermally crosslinkable compound (E).

5. The red-sensitive composition of claim 1 , further comprising an ultraviolet absorber (F).

6. The red-sensitive composition according to claim 1 , further comprising a pigment derivative (G) having basicity.

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

8. 2. The red photosensitive composition according to claim 1, wherein the colorant (A) further comprises at least one selected from the group consisting of a blue colorant (A3) and a purple colorant (A4).

9. The red photosensitive composition according to claim 8, wherein the blue colorant (A3) comprises at least one selected from the group consisting of C.I. Pigment Blue 15:3, C.I. Pigment Blue 15:4, C.I. Pigment Blue 15:6, and C.I. Pigment Blue 16.

10. The red photosensitive composition according to claim 8 , wherein the purple colorant (A4) comprises a compound having a xanthene skeleton.

11. A film formed from the red photosensitive composition according to any one of claims 1 to 8.

12. A color filter comprising the film according to claim 11.

13. A solid-state imaging device comprising the color filter according to claim 12.

14. An image display device comprising the color filter according to claim 12.

Images