Photosensitive composition, film, color filter, solid-state imaging device and image display device

Abstract

To provide a photosensitive composition having excellent pattern formability and capable of forming a film which suppresses reflection of external light.SOLUTION: There is provided a photosensitive composition comprising a coloring material (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D) and an ultraviolet absorber (E), wherein the content of the coloring material (A) is 1 mass% or less in 100 mass% of the non-volatile content of the photosensitive composition, the coloring material (A) includes a purple coloring material (A1) and the content of the purple coloring material (A1) is 50 mass% or more in the 100 mass% of the coloring material (A) and the polymerization initiator (D) does not substantially contain an oxime ester compound.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Color filters used in liquid crystal displays, organic electroluminescence displays, digital cameras, smartphones, infrared sensors, etc. separate the colors of passing light and combine these colors to form an image. Therefore, color filters are required to have high brightness, high contrast, color reproducibility, image reproducibility, etc.

[0003] Solid-state imaging elements and image display devices use three-color filters consisting of red (R), green (G), and blue (B) pixels; however, four-color filters that add a white (W) pixel to the RGB pixels in order to improve brightness and sensitivity have been disclosed (for example, Patent Document 1). The photosensitive composition used to form white pixels has high transparency to light used for exposure, such as i-line light. Therefore, when exposed through a photomask, the unexposed areas around the edges of the mask are also exposed to reflected light or scattered light from the substrate, etc., which tends to increase the line width of the pattern, resulting in a problem of poor pattern formability.

[0004] In order to solve the above problems, for example, Patent Document 2 discloses a photosensitive resin composition containing a resin, an oxime-based photopolymerization initiator, an ultraviolet absorber, and a monomer having a hydrogen bond group, the content of which in the total solid content is 30% by mass or more. Patent Document 3 discloses a radiation-sensitive composition containing a resin, an ultraviolet absorber, and a pigment, the pigments being one or more of a pigment (A) having a maximum absorption wavelength in the range of 400 nm to less than 500 nm, a pigment (B) having a maximum absorption wavelength in the range of 500 nm to less than 600 nm, and a pigment (C) having a maximum absorption wavelength in the range of 600 nm to 700 nm, the total content of all the pigments being 0.1% by mass to 20% by mass or less based on the total solid content. Patent Document 4 discloses a radiation-sensitive composition containing a white or colorless pigment A, an alkali-soluble resin B, a polymerizable compound C having an ethylenically unsaturated double bond, and a polymerizable compound (B) having an absorption coefficient of 1.0×10 at a wavelength of 365 nm in methanol. 3 Photopolymerization initiator D1 has an absorption coefficient of 1.0×10 at a wavelength of 365 nm in methanol. 2 mL / gcm or less, and the extinction coefficient at a wavelength of 254 nm is 1.0 × 10 3 A photosensitive composition is disclosed which contains a photopolymerization initiator D2 having a viscosity of mL / gcm or more, and a mass ratio of the photopolymerization initiator D1 to the photopolymerization initiator D2 is 90:10 to 40:60.

[0005] In addition, in image display devices that use white organic light-emitting diodes (WOLEDs) as a light source, since the electrodes in the WOLEDs are made of metal, color filters with white pixels have the problem of greater external light reflection. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2006-259135 A [Patent Document 2] JP 2010-049029 A [Patent Document 3] JP 2012-208374 A [Patent Document 4] International Publication No. 2018 / 056189 Summary of the Invention [Problem to be solved by the invention]

[0007] However, conventional compositions have insufficient pattern formability and insufficient suppression of external light reflection.

[0008] An object of the present invention is to provide a photosensitive composition which has excellent pattern formability and is capable of forming a film which suppresses external light reflection. [Means for solving the problem]

[0009] <1> The present invention relates to a photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an ultraviolet absorber (E), the content of the color material (A) is 1% by mass or less based on 100% by mass of the nonvolatile content of the photosensitive composition; the color material (A) contains a purple color material (A1), and the content of the purple color material (A1) is 50% by mass or more in 100% by mass of the color material (A); The photosensitive composition further comprises a polymerization initiator (D) that is substantially free of an oxime ester compound. <2> The polymerizable compound (C) contains a polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure. <1> A photosensitive composition comprising: <3> The polymerization initiator (D) contains a compound (D1) represented by the following general formula (1): <1> or <2> A photosensitive composition comprising: General formula (1) [ka] (In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 3 represents a hydrogen atom or a monovalent substituent. <4> The binder resin (B) contains a binder resin (B1) having a thermal crosslinkable group. <1> ~ <3> A photosensitive composition comprising: <5> The purple colorant (A1) includes at least one selected from the group consisting of CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, and a compound having a xanthene skeleton. <1> ~ <4> A photosensitive composition comprising: <6> Further, a polymerization inhibitor (F) is contained. <1> ~ <5> A photosensitive composition comprising: <7> <1> ~ <6> A film formed from the photosensitive composition of claim 1. <8> <7> A color filter having a film. <9> <8> A solid-state imaging device having a color filter. <10> <8> An image display device having a color filter. Effect of the Invention

[0010] According to the present invention, there is provided a photosensitive composition capable of forming a film having excellent pattern formability and capable of suppressing external light reflection. The present invention also provides a film, a color filter, a solid-state imaging device, and an image display device. [Brief description of the drawings]

[0011] [Figure 1] FIG. 1 is a schematic cross-sectional view showing an example of an image display device equipped with a four-color filter having white pixels. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, the embodiment for carrying out the photosensitive 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 the scope of the problem that can be solved.

[0013] 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.

[0014] <Photosensitive composition> A photosensitive composition according to one embodiment of the present invention is a photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an ultraviolet absorber (E), the content of the color material (A) is 1% by mass or less based on 100% by mass of the nonvolatile content of the photosensitive composition; the color material (A) contains a purple color material (A1), and the content of the purple color material (A1) is 50% by mass or more in 100% by mass of the color material (A); The polymerization initiator (D) is characterized in that it does not substantially contain an oxime ester compound.

[0015] The mechanism by which the photosensitive composition of the above configuration can solve the problems of the present invention is not clear, but is speculated as follows. By making the content of the color material (A) 1% by mass or less relative to the total non-volatile content of the photosensitive composition, the brightness and sensitivity of a color filter with white pixels added can be maintained. Furthermore, it is speculated that by making the content of the purple color material (A1) 50% by mass or more in 100% by mass of the color material (A), it is possible to absorb light with a wavelength of about 570 nm contained in white light and suppress external light reflection while maintaining the brightness and sensitivity. And, it is speculated that by not containing a highly sensitive oxime ester compound and containing an ultraviolet absorber (E), the polymerization initiator (D) controls the curing of unintended parts due to halation of exposure, etc., and a stable pattern shape can be obtained.

[0016] Components that are or can be contained in the photosensitive composition of the present invention will be described in detail below.

[0017] Colorant The photosensitive composition of the present invention contains a color material (A), and the content of the color material (A) is 1% by mass or less based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0018] 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, 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.

[0019] 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 solution 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.

[0020] The coloring material (A) can be used alone or in combination of two or more kinds.

[0021] The content of the coloring material (A) is preferably from 0.05 to 0.8% by mass, and more preferably from 0.1 to 0.6% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0022] (Purple color material (A1)) The photosensitive composition of the present invention contains a purple color material (A1), and the content of the purple color material (A1) is 50% by mass or more in 100% by mass of the color material (A).

[0023] The purple colorant (A1) is not particularly limited as long as it is a compound that has absorption at a wavelength of 450 to 620 nm, and any known compound can be used. Examples of the purple colorant (A1) include purple pigments such as CI Pigment Violet 1, 2, 14, 15, 16, 19, 23, 27, 29, 31, 32, 37, 42, 44, 47, 49, 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.

[0024] Further, examples of compounds having a xanthene skeleton include 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, and WO 2019 / 031292 A.

[0025] The purple color material (A1) can be used alone or in combination of two or more kinds.

[0026] The content of the purple color material (A1) is preferably from 50 to 99 mass %, and more preferably from 60 to 95 mass %, in 100 mass % of the color material (A).

[0027] From the viewpoint of suppressing reflection of external light, the purple colorant (A1) preferably contains one or more selected from the group consisting of CI Pigment Violet 19, 23, 29, and compounds having a xanthene skeleton, and from the viewpoint of maintaining luminance and sensitivity and suppressing roughness of the pattern surface in a post-bake step, it is more preferable that the purple colorant (A1) contains a compound having a xanthene skeleton.

[0028] From the viewpoint of suppressing aggregation of coloring materials, the compound having a xanthene skeleton is 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.

[0029] The resin that forms a salt with one or more dyes selected from CI Acid Red 52,289,463 (hereinafter, simply referred to as a salt-forming resin) is preferably a resin having a monomer unit represented by the following general formula (2).

[0030] General formula (2) [ka]

[0031] In general formula (2), R 1 ~R 3each independently represents a hydrogen atom or a linear or cyclic hydrocarbon group which may have a substituent; R 1 ~R 3 Two or more of R may be bonded to each other to form a ring structure. 4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, Y - indicates a counter anion.

[0032] R in general formula (2) 1 ~R 3 is more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group.

[0033] The divalent linking group X in the general formula (2) is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R 13 -,-COO-R 14 -(However, R 13 and R 14 is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms), and preferably -COO-R 14 -It is.

[0034] The counter anion Y in the general formula (2) - may be an inorganic or organic anion. Examples of the counter anion include hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, and permanganate ions; and complex ions such as ferricyanide (III) ions. Among these, halogen ions and carboxylate ions are preferred, and halogen ions are more preferred.

[0035] Examples of monomers forming the monomer unit represented by general formula (2) include alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl triethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, and (meth)acryloyloxyethyl methyl morpholino ammonium chloride; alkyl (meth)acryloyl amide-based quaternary ammonium salts such as (meth)acryloyl aminopropyl trimethyl ammonium chloride, (meth)acryloyl aminoethyl triethyl ammonium chloride, and (meth)acryloyl aminoethyl dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl sulfate; and trimethyl vinyl phenyl ammonium chloride.

[0036] The method for producing a resin having a monomer unit represented by general formula (2) is not limited to a method of copolymerizing a monomer represented by general formula (2), but may also involve reacting a resin obtained by polymerizing an amino group-containing monomer with an onium chloride agent to form an ammonium salt.

[0037] The monomer unit represented by formula (2) can be used alone or in combination of two or more kinds.

[0038] The salt forming resin may contain a monomer unit other than the monomer unit represented by the general formula (2) (hereinafter, other monomer unit). The other monomer unit is not particularly limited, and may be a monomer copolymerizable with the monomer forming the monomer unit represented by the general formula (2).

[0039] Examples of other monomers include monomers that can be used in the synthesis of the binder resin (B1) described below.

[0040] Examples of the structure of the salt forming resin include a random structure, a block structure, a graft structure, a comb structure, a star structure, etc. Among these, the block structure is preferred from the viewpoint of suppressing aggregation of the coloring material.

[0041] The method for producing the salt-forming compound of the dye and the resin that forms a salt is not particularly limited, and any known method can be used. For example, the methods described in paragraphs 0360 to 0371 of JP-A-2015-28587 and paragraph 0135 of JP-A-2018-172542 can be mentioned.

[0042] The content of the compound having a xanthene skeleton is preferably 50% by mass or more, and more preferably from 50 to 95% by mass, in 100% by mass of the purple color material (A1).

[0043] The photosensitive composition of the present invention may contain, as the colorant (A), a colorant other than the purple colorant (A1).

[0044] The coloring materials other than the purple coloring material (A1) are not particularly limited and may be any known compound. For example, chromatic coloring materials such as blue, green, red, yellow, and orange coloring materials, and achromatic coloring materials such as white and black coloring materials may be used. Among these, the blue colorant (A2) is preferred from the viewpoint of suppressing reflection of external light.

[0045] (Blue color material (A2)) The blue colorant (A2) 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, the blue colorant (A2) preferably contains 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.

[0046] The blue colorant (A2) can be used alone or in combination of two or more kinds.

[0047] The content of the blue color material (A2) is preferably from 1 to 30 mass %, and more preferably from 5 to 20 mass %, in 100 mass % of the color material (A).

[0048] (Green color material) The green coloring material is not particularly limited, and any known compound can be used. For example, CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 63, 64, 65, 66, and the like can be mentioned. Further examples include dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, and CI Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, as well as lake compounds, salt-forming compounds, and polymers of these dyes. Further, compounds described in JP-A-05-345861, JP-A-2000-281927, JP-A-2010-265254, JP-A-2015-060184, WO 2023 / 002875, and WO 2023 / 136027 are also included.

[0049] (Red color material) The red colorant 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, 63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181, 184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,2 No. 62,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282,283,284,285,286,287,291,295,296,297, JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Further examples include 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 dyes.

[0050] (yellow color material) The yellow coloring material 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, 139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,174,175,176,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233,234,235,236, yellow pigments described in JP-A-2012-226110, and yellow pigments described in JP-A-2019-113676.

[0051] 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 (3) 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 (4).

[0052] General formula (3) [ka]

[0053] In the general formula (3), two R 1 are each independently -OH, -NH 2 , -NH-CN, an acylamino group, an alkylamino group, or an arylamino group; 2 are each independently -OH or -NH 2Represents.

[0054] General formula (4) [ka]

[0055] In the general formula (4), three R 3 each independently represents a hydrogen atom or an alkyl group.

[0056] 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.

[0057] 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.

[0058] (orange color material) The orange colorant is not particularly limited, and any known compound can be used. For example, CI Pigment Orange 13, 36, 38, 43, 64, 71, 72, 73, and other pigments can be used.

[0059] (white color material) The white coloring material is not particularly limited, and known compounds can be used. For example, CI Pigment White 1, 2, 3, 4, 5, 6, 6:1, 7, 8, 10, 11, 12, 13, 14, 15, 16, 17, 18, 18:1, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 30, 32, 33, etc. can be mentioned.

[0060] (Black color material) The black coloring material is not particularly limited, and known compounds can be used, such as CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0061] [Binder resin (B)] The photosensitive composition of the present invention contains a binder resin (B).

[0062] The binder resin (B) is not particularly limited as long as it is soluble in the alkaline developer described below, and a known resin can be used. Examples of the resin type of the binder resin (B) include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamideimide resin, cyclic olefin resin, polysiloxane resin, etc.

[0063] The binder resin (B) preferably has an acidic group. Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group. Among these, a carboxyl group is more preferable from the viewpoint of pattern formability.

[0064] The weight average molecular weight of the binder resin (B) is preferably 3,000 to 50,000.

[0065] The acid value of the binder resin (B) is preferably from 30 to 200 mgKOH / g, and more preferably from 40 to 180 mgKOH / g.

[0066] The binder resin (B) can be used alone or in combination of two or more kinds.

[0067] The binder resin (B) is preferably from 1 to 80 mass %, more preferably from 5 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0068] (Binder resin (B1) having a thermally crosslinkable group) From the viewpoint of suppressing the roughening of the pattern surface in the post-baking step, the binder resin (B) preferably contains a binder resin (B1) having a thermal crosslinking group (hereinafter, also simply referred to as binder resin (B1)). It is presumed that the thermal crosslinking group causes a crosslinking reaction during post-baking and suppresses the movement of the pattern surface due to thermal melting.

[0069] The thermally crosslinkable group is a group that undergoes a crosslinking reaction upon heating to form a crosslink, and examples thereof 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.

[0070] The binder resin (B1) is not particularly limited, and any known resin can be used. For example, a copolymer of a thermocrosslinkable group-containing monomer and any other copolymerizable monomer can be used.

[0071] The thermally crosslinkable group-containing monomer is preferably a monomer represented by the following general formula (5) from the viewpoint of suppressing roughening of the pattern surface in the post-bake step.

[0072] General formula (5) [ka]

[0073] In general formula (5), R 1 represents a hydrogen atom or a methyl group.

[0074] In general formula (5), 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 bond. The alkylene group having 1 to 20 carbon atoms may be any of linear, branched, and combinations thereof, and examples thereof include a methylene group, an ethylene group, an n-propyl group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an isopropylene group, a 2-methylpropylene group, a 2-methylhexylene group, and a tetramethylethylene group.

[0075] In general formula (5), X 1 represents a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group means a group having a cyclic structure in which an epoxy group and a saturated hydrocarbon ring are condensed. The cyclic ether group is preferably an oxetanyl group from the viewpoints of suppressing roughening of the pattern surface in the post-bake step and suppressing aggregation of the coloring material.

[0076] Specific examples of the monomer represented by the general formula (5) include glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0]phenylmethyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3,4-epoxycyclo[5.2.1.0]phenyl ... 2,6 ]Decan-8-yl (meth)acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Examples of the compound include compounds having an epoxy group such as decan-9-yl (meth)acrylate. Examples of compounds having an oxetanyl group include 3-((meth)acryloyloxymethyl)oxetane, 3-((meth)acryloyloxymethyl)-3-ethyloxetane, 3-((meth)acryloyloxymethyl)-2-methyloxetane, 3-((meth)acryloyloxyethyl)-3-ethyloxetane, 2-ethyl-3-((meth)acryloyloxyethyl)oxetane, 3-methyl-3-(meth)acryloyloxymethyloxetane, and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

[0077] Examples of other monomers copolymerizable with the thermally crosslinkable group-containing monomer (hereinafter also referred to as other monomers) 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-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexyl hydrophthalic acid, p -styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, 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, 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 para-cumylphenol, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, styrene, α-methylstyrene, p-vinyltoluene, p-chlorostyrene, vinylnaphthalene, (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acryl Amides, 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 ester, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 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, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and the like.

[0078] The content of the thermally crosslinkable group-containing monomer unit is preferably from 1 to 80 mass %, more preferably from 5 to 70 mass %, of all the monomer units constituting the binder resin (B1).

[0079] Examples of the structure of the binder resin (B1) include a random structure, a block structure, a graft structure, a comb structure, and a star structure, etc. Among these, the comb structure is preferred from the viewpoints of suppressing the roughening of the pattern surface in the post-bake step and suppressing the aggregation of the coloring material.

[0080] From the viewpoint of suppressing roughening of the pattern surface in the post-bake step and suppressing aggregation of the colorant, the binder resin (B1) 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 moiety of 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 copolymer moiety with a thermally crosslinkable group-containing monomer and other monomers.

[0081] 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 simultaneously with the formation of an ester bond.

[0082] The copolymer moiety containing the thermally crosslinkable group in the side chain and the other monomer can be obtained, for example, by the following two methods. The first method is a method of copolymerizing a thermally crosslinkable group-containing monomer and other monomers 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 thermally crosslinkable group-containing monomer and other monomers are 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.

[0083] The main chain and the side chain will be described in detail below.

[0084] [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.

[0085] Examples of aromatic compounds having two or more acid anhydride groups include compounds represented by the following general formulas (6) and (7).

[0086] [ka]

[0087] In formula (6), n represents 1 or 2. In general formula (7), Q is a direct bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, a group represented by the following general formula (8), or a group represented by the following general formula (9):

[0088] [ka]

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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. Theoretically, when the aromatic compound having two or more acid anhydride groups exceeds 1 mole, the terminal becomes an acid anhydride group.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] [Side Chain] The copolymer moiety with the thermally crosslinkable group-containing monomer in the side chain and the other monomer can be synthesized by a method of copolymerizing the thermally crosslinkable group-containing monomer and the other monomer in the presence of a compound having two or more hydroxyl groups, as described above, or a method of copolymerizing the thermally crosslinkable group-containing monomer and the other monomer in the presence of a reaction product between an aromatic compound having two or more acid anhydride groups and the hydroxyl groups of a compound having two or more hydroxyl groups.

[0097] Examples of the thermally crosslinkable group-containing monomer and other monomers include the monomers described above.

[0098] The synthesis method is preferably, for example, to radically polymerize a thermally crosslinkable group-containing monomer and other monomers in the presence of a compound (a) having two or more hydroxyl groups, i.e., a compound having two hydroxyl groups at one end and one thiol group, to generate a polymer of the thermally crosslinkable group-containing monomer having two hydroxyl groups at one end and the other monomers, and then react it with a tetracarboxylic dianhydride (b), 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 it with a monoalcohol.

[0099] [ka]

[0100] 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.

[0101] The polymerization temperature of the thermally crosslinkable group-containing monomer and the copolymer portion with other monomers is preferably 40 to 150° C., more preferably 50 to 110° C. If it is 40° C. or higher, the polymerization easily proceeds, and if it is 150° C. or lower, it is easy to control the molecular weight.

[0102] When polymerizing the copolymer portion with the thermal crosslinking group-containing monomer and other monomers, 0.001 to 5 mass% of a polymerization initiator can be used based on the total monomer mass. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0103] 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.

[0104] The copolymer portion of the thermal crosslinkable group-containing monomer and other monomers is preferably synthesized by bulk polymerization or solution polymerization. Examples of polymerization solvents for solution polymerization include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, but are not limited thereto. These polymerization solvents can be used alone or in combination of two or more.

[0105] 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.

[0106] 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.

[0107] The synthesis temperature for the aromatic carboxylate moiety is preferably from 50 to 180°C, more preferably from 80 to 140°C.

[0108] The acid value of the binder resin (B1) is preferably from 30 to 250 mgKOH / g, more preferably from 40 to 200 mgKOH / g.

[0109] The weight average molecular weight of the binder resin (B1) is preferably from 2,000 to 50,000, and more preferably from 4,000 to 40,000.

[0110] The binder resin (B1) can be used alone or in combination of two or more kinds.

[0111] The content of the binder resin (B1) is preferably 500 parts by mass or more, and more preferably 1,000 parts by mass or more, based on 100 parts by mass of the color material (A).

[0112] (Binder resin (B2) other than binder resin (B1)) The binder resin (B) can contain a binder resin (B2) other than the binder resin (B1) (hereinafter, also simply referred to as other binder resin (B2)).

[0113] [Polymerizable compound (C)] The photosensitive composition of the present invention contains a polymerizable compound (C).

[0114] The polymerizable compound (C) may be a monomer or oligomer having a polymerizable unsaturated group, such as a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, or a styryl group.

[0115] The polymerizable compound (C) may be used alone or in combination of two or more kinds.

[0116] The content of the polymerizable compound (C) is preferably from 30 to 90 mass%, more preferably from 40 to 80 mass%, particularly preferably from 50 to 70 mass%, based on 100 mass% of the nonvolatile content of the photosensitive composition.

[0117] (Multifunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure) From the viewpoint of adhesion, the polymerizable compound (C) preferably contains a multifunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure. This is believed to form a chemical crosslinked structure by polymerization as well as a physical crosslinked structure by intermolecular hydrogen bonds between urethane bonds or functional groups of the substrate, and further, the amine structure interacts with the substrate and other components, improving adhesion. The amine structure of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary 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.

[0118] The polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure preferably has 2 to 60 (meth)acryloyl groups.

[0119] The weight average molecular weight of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is preferably from 500 to 50,000, and more preferably from 1,000 to 30,000.

[0120] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is preferably 1.5-5.

[0121] The acid value of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is preferably 10 mgKOH / g or less.

[0122] The polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure can be used alone or in combination of two or more kinds.

[0123] The content of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is preferably from 0.1 to 80 mass %, more preferably from 0.5 to 60 mass %, in 100 mass % of the polymerizable compound (C).

[0124] The polyfunctional urethane (meth)acrylate (C1) having a secondary or tertiary amine structure can be synthesized as follows: For example, it can be synthesized by a urethane reaction between a Michael addition reaction product (precursor) of a (meth)acrylate compound (X) and an amine compound (Y) having a hydroxyl group, and a polyisocyanate compound (Z).

[0125] Examples of the (meth)acrylate compound (X) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane EO or PO-modified tri(meth)acrylate, ditrimethylolpropane EO or PO-modified tetra(meth)acrylate, pentaerythritol EO or PO-modified tetra(meth)acrylate, and dipentaerythritol EO or PO-modified hexa(meth)acrylate.

[0126] The (meth)acrylate compounds (X) can be used alone or in combination of two or more.

[0127] Examples of the amine compound (Y) having a hydroxyl group include ethanolamine, butanolamine, diethylene glycolamine, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminobenzyl alcohol, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, N-butyl-4-hydroxybutylamine, and N-(2-hydroxyethyl)piperazine.

[0128] The amine compound (Y) having a hydroxyl group can be used alone or in combination of two or more kinds.

[0129] The method of the Michael addition reaction between the (meth)acrylate compound (X) and the amine compound (Y) having a hydroxyl group is not particularly limited, and a known method can be used. For example, the methods described in International Publication No. 2006 / 075754, JP-T-2008-545859, JP-A-2017-066347, JP-T-2018-517797, etc. can be mentioned.

[0130] 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 examples of such compounds include biuret compounds, isocyanurate compounds, adduct compounds, allophanate compounds, and the like.

[0131] The polyisocyanate compounds (Z) can be used alone or in combination of two or more kinds.

[0132] 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.

[0133] From the viewpoint of pattern formability, the multifunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is more preferably at least one selected from the group consisting of aliphatic multifunctional urethane (meth)acrylates having a secondary amine or tertiary amine structure, and alicyclic multifunctional urethane (meth)acrylates having a secondary amine or tertiary amine structure.

[0134] The aliphatic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure can be obtained by using a polyisocyanate compound having an aliphatic structure as the above-mentioned polyisocyanate compound (Z).

[0135] The alicyclic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure can be obtained by using a polyisocyanate compound having an alicyclic structure as the above-mentioned polyisocyanate compound (Z).

[0136] An example of a commercially available product of the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is CN9906NS manufactured by Arkema.

[0137] (Meth)acrylate (C2) other than polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure) From the viewpoint of pattern formability, the polymerizable compound (C) preferably contains a (meth)acrylate (C2) other than the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure (hereinafter also simply referred to as other (meth)acrylate (C2)).

[0138] Examples of the other (meth)acrylates (C2) include (meth)acrylates having a hydroxyl group, (meth)acrylates having an acidic group, lactone-modified (meth)acrylates, (meth)acrylates having a urethane bond, (meth)acrylates having an amine structure, and (meth)acrylates having a dendrimer structure or a hyperbranched structure. In this specification, the polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure is not included in the (meth)acrylate having a urethane bond and the (meth)acrylate having an amine structure.

[0139] The number of (meth)acryloyl groups in the other (meth)acrylate (C2) is preferably 5 or less, more preferably 4 or less, from the viewpoint of pattern formability.

[0140] The other (meth)acrylates (C2) can be used alone or in combination of two or more kinds.

[0141] The content of the other (meth)acrylate (C2) is preferably from 20 to 99.9% by mass in 100% by mass of the polymerizable compound (C).

[0142] [(Meth)acrylate having a hydroxyl group] Examples of the (meth)acrylate 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 such acrylic acid esters 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, and dipentaerythritol caprolactone-modified penta(meth)acrylate; and epoxy (meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid.

[0143] Examples of commercially available (meth)acrylates 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.

[0144] [(Meth)acrylate having an acidic group] Examples of the (meth)acrylate having an acidic group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like.

[0145] Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0146] Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.

[0147] 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.

[0148] Commercially available products of (meth)acrylates 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.

[0149] [Lactone-modified (meth)acrylate] Lactone-modified (meth)acrylates are (meth)acrylates having a structure modified with lactone in the molecule. Lactone-modified (meth)acrylates are obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethylthritol, tripentaerythritol, glycerin, diglycerol, and trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0150] Commercially available lactone-modified (meth)acrylate products include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0151] [(Meth)acrylate having a urethane bond] Examples of the (meth)acrylate having a urethane bond include a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a polyisocyanate, and a compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the resulting mixture with a (meth)acrylate having a hydroxyl group.

[0152] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide (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.

[0153] Examples of the polyisocyanate 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, isocyanate nurate forms, adduct forms, allophanates, and the like thereof.

[0154] From the viewpoint of developability, it is preferable that the (meth)acrylate having a urethane bond further has 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 preferable.

[0155] The method for introducing an acidic group into a (meth)acrylate 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.

[0156] 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.

[0157] Commercially available (meth)acrylates 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.

[0158] [(Meth)acrylate having an amine structure] The amine structure of the (meth)acrylate having an amine structure may be any of a primary amine, secondary amine, and tertiary amine structures, and is preferably a secondary amine or tertiary amine, but 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.

[0159] Examples of the (meth)acrylate having an amine structure include tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, and tris(2-hydroxy-3-methacryloyloxypropyl)amine.

[0160] Commercially available products of (meth)acrylates having an amine structure include EBECRYL80 and 7100 manufactured by Daicel-Allnex Co., Ltd., CN371NS, 372, 374, 383, and 386 manufactured by Arkema Co., Ltd., and Aronix MT-3041 and 3042 manufactured by Toagosei Co., Ltd.

[0161] [(Meth)acrylate having a dendrimer structure or a hyperbranched structure] (Meth)acrylates with a dendrimer structure have a chemical structure in which the core-constituting chemical structure (hereinafter also referred to as the core portion) is regularly branched outward, with (meth)acryloyl groups bonded to the ends of the branches, and have a highly controlled spherical chemical structure and molecular weight. The hyperbranched structure has a chemical structure similar to that of a dendrimer structure.

[0162] Commercially available (meth)acrylates having a dendrimer structure or a hyperbranched structure include, for example, Viscoat #1000LT (dendrimer structure, average number of acryloyl groups: 14) manufactured by Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average number of acryloyl groups: 18) and Miramer 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), and Eternal Examples of such copolymers include Etercure 6361-100 (hyperbranched structure, average number of acryloyl groups: 8), Etercure 6362-100 (hyperbranched structure, average number of acryloyl groups: 12), Etercure 6363 (hyperbranched structure, average number of acryloyl groups: 16), and Etercure DR-E522 (hyperbranched structure, average number of acryloyl groups: 15), all of which are manufactured by Materials.

[0163] In addition to the above, other (meth)acrylates (C2) include, for example, 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, glycerol tri(meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO, Examples of the (meth)acrylic acid ester include modified or PO-modified tri(meth)acrylate, isocyanuric acid EO-modified 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 various (meth)acrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0164] Commercially available products 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-211B manufactured by Toagosei Co., Ltd. M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460, M-930, 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.

[0165] 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.

[0166] [Polymerization initiator (D)] The photosensitive composition of the present invention contains a polymerization initiator (D), and the polymerization initiator (D) does not substantially contain an oxime ester compound. The polymerization initiator (D) may be a known compound. For example, a compound that generates radicals by the action of light or heat to initiate or promote a radical polymerization reaction may be used. In the present invention, "substantially free of oxime ester compounds" refers to the case where the oxime ester compounds are unintentionally mixed in during the preparation of the photosensitive composition. The content of the oxime ester compounds is 0.1% by mass or less, preferably 0.05% by mass or less, and more preferably 0.01% by mass or less, based on 100% by mass of the polymerization initiator (D).

[0167] The polymerization initiator (D) can be used alone or in combination of two or more kinds.

[0168] The content of the polymerization initiator (D) is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0169] (Compound (D1) represented by general formula (1)) From the viewpoint of pattern formability, the polymerization initiator (D) preferably contains a compound (D1) represented by the following general formula (1). The compound (D1) represented by the general formula (1) has a lower sensitivity to ultraviolet light than an oxime ester compound, and can further suppress changes in line width due to halation of exposure. In addition, the cured film has an appropriate cohesive force due to the π-π interaction between the two benzene rings of the fluorene skeleton. Therefore, the cross-sectional shape of the pattern can be improved by appropriate heat sagging while suppressing surface roughness of the pattern due to thermal melting in the post-bake process.

[0170] General formula (1) [ka]

[0171] In general formula (1), R 1 and R 2 R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 3 represents a hydrogen atom or a monovalent substituent.

[0172] In general formula (1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Among these, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0173] In general formula (1), R 3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include an alkyl group having 1 to 20 carbon atoms, such as a methyl group or an ethyl group; an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group or an ethoxy group; a halogen atom, such as F, Cl, Br, or I; an acyl group having 1 to 20 carbon atoms; an alkyl ester group having 1 to 20 carbon atoms; an alkoxycarbonyl group having 1 to 20 carbon atoms; a halogenated alkyl group having 1 to 20 carbon atoms, an aromatic ring group having 4 to 20 carbon atoms; an amino group; an aminoalkyl group having 1 to 20 carbon atoms; a hydroxyl group; a nitro group; a cyano group; a benzoyl group which may have a substituent; and a thenoyl group which may have a substituent. Examples of the substituent that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxycarbonyl group having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom or a nitro group is preferable, and a hydrogen atom is more preferable.

[0174] Examples of methods for producing the compound represented by general formula (1) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0175] Specific examples of the compound (D1) represented by formula (1) are shown below, but the present invention is not limited thereto.

[0176] [ka]

[0177] The compound (D1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0178] The content of the compound (D1) represented by the general formula (1) is preferably from 10 to 100% by mass in 100% by mass of the polymerization initiator (D).

[0179] (Polymerization initiator (D2) other than the compound (D1) represented by general formula (1)) The polymerization initiator (D) can contain a polymerization initiator (D2) other than the compound (D1) represented by general formula (1) (hereinafter, also simply referred to as other polymerization initiator (D2)).

[0180] Other polymerization initiators (D2) can be classified as follows: The photopolymerization initiator is a polymerization initiator that generates radicals by light, and is preferably a compound that generates radicals by light in the ultraviolet to visible light range. The thermal polymerization initiator is a polymerization initiator that generates radicals by heat, and may be a compound that generates radicals by the action of heat and light.

[0181] Examples of the photopolymerization initiator include α-hydroxyketone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, and 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; α-aminoketone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, and 2-dimethylamino-2-(4-methylbenzyl)-1-[4-(morpholinophenyl)-butan-1-one; Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 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; Examples of the quinone compounds include 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0182] Commercially available products include Omnirad 127, 184, 1173, and 2959 manufactured by IGM Resins as α-hydroxyketone compounds, Omnirad 907, 369E, and 379EG manufactured by IGM Resins as α-aminoketone compounds, and Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine compounds.

[0183] 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; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxides include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide. Further examples include oxime sulfonate compounds described in WO 2012 / 101245, WO 2016 / 030790, and the like.

[0184] [Ultraviolet absorber (E)] The photosensitive composition of the present invention contains an ultraviolet absorber (E).

[0185] The ultraviolet absorbent (E) is not particularly limited, and known compounds can be used. For example, compounds having a maximum absorption wavelength in the wavelength range of 300 to 400 nm are preferred, and examples thereof include benzophenone compounds, benzotriazole compounds, triazine compounds, conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, acrylonitrile compounds, benzothiazole compounds, and salicylate compounds.

[0186] The ultraviolet absorbents (E) can be used alone or in combination of two or more kinds.

[0187] The content of the ultraviolet absorber (E) is preferably from 50 to 2,000 parts by mass, and more preferably from 100 to 1,000 parts by mass, based on 100 parts by mass of the color material (A).

[0188] From the viewpoint of pattern formability, the ultraviolet absorber (E) preferably contains one or more compounds selected from the group consisting of triazine compounds (E1), benzotriazole compounds (E2), and benzophenone compounds (E3), and more preferably a triazine compound (E1).

[0189] (Triazine compound (E1)) Examples of the triazine compound (E1) 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, Examples of the 4-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. The triazine compound (E1) preferably contains at least one selected from the group consisting of the compounds represented by the following (E1-1) to (E1-5).

[0190] [ka]

[0191] (Benzotriazole compound (E2)) Benzotriazole compounds (E2) 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 linear alkyl), 2-[5-chloro-(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol, 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. The benzotriazole compound (E2) preferably contains one or more compounds selected from the group consisting of the compounds represented by the following (E2-1) to (E2-5).

[0192] [ka]

[0193] (Benzophenone compounds (E3)) Examples of the benzophenone compound (E3) 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. The benzophenone compound (E3) preferably contains one or more compounds selected from the group consisting of the compounds represented by the following (E3-1) to (E3-4).

[0194] [ka]

[0195] [Polymerization inhibitor (F)] From the viewpoint of pattern formability, the photosensitive composition of the present invention preferably contains a polymerization inhibitor (F), which can control unintended curing due to halation of exposure and the like, thereby further improving pattern formability.

[0196] The polymerization inhibitor (F) is not particularly limited, and a known compound can be used. For example, phenol compounds, hydroquinone compounds, benzoquinone compounds, phenothiazine compounds, catechol compounds, nitrobenzene compounds, nitroso compounds, amine compounds, hindered amine compounds, phosphorus compounds, etc. can be mentioned. Among these, it is preferable to include a hydroquinone compound.

[0197] Examples of the phenol compound include p-methoxyphenol, 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, triethylene glycol-bis[3-(3-t pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione, and the like.

[0198] Examples of the hydroquinone compound include hydroquinone, methylhydroquinone, ethylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,3,5-trimethylhydroquinone, and 2,5-dichlorohydroquinone.

[0199] Examples of the benzoquinone compound include p-benzoquinone, methyl-p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2,5-diphenyl-p-benzoquinone, chloro-p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, tetrachloro-p-benzoquinone, and tetrabromo-p-benzoquinone.

[0200] Examples of the phenothiazine compound include phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 10-methylphenothiazine, and 2-methoxyphenothiazine.

[0201] Examples of the catechol compound include 4-methylcatechol, 4-tert-butylcatechol, and 3,5-di-tert-butylcatechol.

[0202] Examples of the nitrobenzene compound include nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrotoluene, dinitrodurene, and 2,2-diphenyl-1-picrylhydrazyl.

[0203] Examples of nitroso compounds include nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, and 4-nitroso-diphenylamine.

[0204] Examples of the amine compound include N,N-diphenylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyldiphenylamine, 4-aminodiphenylamine, p-nitrosodiphenylamine, N-nitrosodinaphthylamine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosophenylhydroxylamine, N,N'-dialkyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, Examples of such diamines include N-phenyl-N'-isopropyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, N,N-diethylhydroxylamine, 1,4-benzenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-benzenediamine, and N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine.

[0205] Examples of the hindered amine compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethyl-1-hydroxypiperidine, 4-oxo-2,2,6,6-tetramethylpiperidine-1-oxyl, and 4-oxo-2,2,6,6-tetramethyl-1-oxypiperidine.

[0206] Examples of phosphorus compounds include triphenylphosphine, triphenylphosphite, triethylphosphite, tris(isodecyl)phosphite, tris(tridecyl)phosphite, phenyldiisooctylphosphite, phenyldiisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenylisodecylphosphite, diphenyltridecylphosphite, phosphonic acid [1,1-diphenyl-4,4'-diylbistetrakis-2,4-bis(1,1-dimethylethyl)phenyl] ester, triphenylphosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidenediphenol alkylphosphite, tris(2,4-di- tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, and the like.

[0207] The polymerization inhibitor (F) can be used alone or in combination of two or more kinds.

[0208] The content of the polymerization inhibitor (F) is preferably from 0.01 to 0.5% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0209] [Pigment derivatives (G)] The photosensitive composition of the present invention can contain a pigment derivative (G).

[0210] The pigment derivative (G) is not particularly limited, and known compounds can be used. For example, compounds having a structure in which a part of the pigment is substituted with an acidic group, a basic group, a neutral group, etc. can be mentioned. Specifically, compounds having acidic substituents such as sulfo groups, carboxy groups, and phosphoric acid groups, and amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminals, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups can be mentioned. Examples of types of pigments 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, and naphthalocyanine compounds.

[0211] The pigment derivative (G) is preferably added during the micronization of the color material (A) described above, or during the dispersion treatment of the color material (A) described below. The average primary particle size of the pigment derivative (G) is preferably 5 to 200 nm.

[0212] The pigment derivative (G) can be used alone or in combination of two or more kinds.

[0213] The content of the 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).

[0214] [Dispersion resin (H)] The photosensitive composition of the present invention may contain a dispersing resin (H). In this specification, the dispersing resin (H) is used when preparing a colorant dispersion. The binder resin (B) is used when blending the polymerizable compound (C) and the polymerization initiator (D).

[0215] The dispersing resin (H) is preferably a resin having an adsorptive group having a high affinity for the colorant (A). The adsorptive group preferably has at least one type of basic group and acidic group.

[0216] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0217] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group.

[0218] Examples of the resin type of the dispersion resin (H) include urethane resins, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylates, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0219] Examples of the structure of the dispersing resin (H) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0220] Commercially available dispersion resins (H) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, and 2095 manufactured by BYK Japan Co., Ltd. ,2150,2155,2163,2164, or Anti-Terra-U203,204, or BYK-P104,P104S,220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000,9000,13000,13240,13650,13940,16000,17000,18000,20000,21000,24000,26 000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Aji Super PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, and paragraphs 0122 to 0155 of WO 2013175978 A, the resins described in paragraphs 0317 to 0321 of JP 2019-78878 A, and paragraph 00 of WO 2018 / 139534 A are also usable. 83, the resins described in paragraphs 0167 to 0191 of WO 2019 / 163505, the resins described in paragraphs 0299 ​​to 0310 of WO 2021 / 131927, the resins described in paragraphs 0080 to 0085 of WO 2022 / 102367, and the resins described in paragraphs 0099 to 0109 of WO 2022 / 172607.

[0221] The dispersing resin (H) can be used alone or in combination of two or more kinds.

[0222] The content of the dispersing resin (H) is preferably from 3 to 200 parts by mass, and more preferably from 5 to 150 parts by mass, based on 100 parts by mass of the coloring material (A).

[0223] [Sensitizer (I)] The photosensitive composition of the present invention can contain a sensitizer (I).

[0224] The sensitizer (I) is not particularly limited, and known compounds can be used. For example, polymethine dyes such as chalcone compounds, unsaturated ketones such as dibenzalacetone, 1,2-diketone compounds such as benzil and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, and oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, sucrose compounds, etc. Examples of the compound include allylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalylporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyrylium-based compounds, thiopyrylium-based compounds, tetraphylline-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, and benzophenone-based compounds.

[0225] The sensitizers (I) can be used alone or in combination of two or more kinds.

[0226] The content of the sensitizer (I) is preferably from 5 to 200 parts by mass, and more preferably from 10 to 150 parts by mass, based on 100 parts by mass of the polymerization initiator (D).

[0227] [Thermal crosslinkable compound (J)] The photosensitive composition of the present invention may contain a thermally crosslinkable compound (J). In this specification, the thermally crosslinkable compound (J) is a compound having no carboxyl group and no polymerizable unsaturated group, and is different from the binder resin (B) and the polymerizable compound (C).

[0228] The thermal crosslinking compound (J) 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, from the viewpoint of suppressing the roughness of the pattern surface in the post-bake process, a compound having an epoxy group and a compound having a blocked isocyanate group are preferred.

[0229] The thermally crosslinkable compound (J) can be used alone or in combination of two or more kinds.

[0230] The content of the thermally crosslinkable compound (J) 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 photosensitive composition.

[0231] (Compounds having epoxy groups) 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.

[0232] Examples of commercially available products of compounds having an epoxy group include Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and 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.

[0233] The compound having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0234] The epoxy equivalent of the compound 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.

[0235] The compound having an epoxy group preferably includes a compound represented by the following general formula (10).

[0236] General formula (10) [ka]

[0237] In formula (10), 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.

[0238] 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 (10) may be the same or different.

[0239] The compound represented by the general formula (10) 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.

[0240] The compounds having an epoxy group can be used alone or in combination of two or more kinds.

[0241] The content of the compound having an epoxy group is preferably from 0.5 to 40% by mass, and more preferably from 1 to 30% by mass, based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0242] (Compounds having blocked isocyanate groups) The compound 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.

[0243] The compound 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.

[0244] 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. The elimination temperature of the active methylene compound or the temperature of the transesterification reaction is low at 80 to 110°C, and the reaction is sufficient.

[0245] 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.

[0246] 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.

[0247] Examples of compounds 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.

[0248] [ka]

[0249] 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.

[0250] [ka]

[0251] Examples of commercially available compounds having an aliphatic structure that have a blocked isocyanate group 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.

[0252] The compound having a blocked isocyanate group preferably has 1 to 20 blocked isocyanate groups, and more preferably has 2 to 15 blocked isocyanate groups.

[0253] The weight average molecular weight of the compound having a blocked isocyanate group is preferably from 300 to 5,000, and more preferably from 500 to 3,000.

[0254] The compound having a blocked isocyanate group can be used alone or in combination of two or more kinds.

[0255] The content of the compound having a blocked isocyanate group 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 photosensitive composition.

[0256] [Thiol-based chain transfer agent (K)] The photosensitive composition of the present invention may contain a thiol chain transfer agent (K).

[0257] The thiol-based chain transfer agent (K) is not particularly limited, and known compounds can be used. For example, 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)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine.

[0258] The thiol chain transfer agent (K) can be used alone or in combination of two or more kinds.

[0259] The content of the thiol chain transfer agent (K) is preferably from 0.1 to 10% by mass in 100% by mass of the nonvolatile content of the photosensitive composition.

[0260] [Silane coupling agent (L)] The photosensitive composition of the present invention may contain a silane coupling agent (L).

[0261] The silane coupling agent (L) is a compound having a hydrolyzable group. The hydrolyzable group is a group that is directly bonded to a silicon atom and generates a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group. Among these, an alkoxy group is preferred. From the viewpoint of reactivity, the alkoxy group is preferably a methoxy group or an ethoxy group. The silane coupling agent (L) may have a reactive functional group other than the hydrolyzable group. Examples of the reactive functional group 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.

[0262] The silane coupling agent (L) is not particularly limited, and known compounds can be used. For example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, Silane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, 3-ureidopropyltrialkoxysilane, N,N-bis[3-(trimethoxysilyl)propyl]ethylenediamine, bis(3-triethoxysilyl)propyl)tetrasulfide, 1,6-bis(trimethoxysilyl)hexane, 1,8-bis(trimethoxysilyl)octane, tris(-trimethoxysilylpropyl)isocyanate, and the like.

[0263] Commercially available silane coupling agents (L) 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, KBE-1003, and KBM-5 manufactured by Shin-Etsu Chemical Co., Ltd. 02, KBM-503, KBE-502, KBE-503, KBM-5803, X-12-1048, X-12-1050, KBE-9007N, KBM-9659, KBM-802, KBM-803, KBM-1043, KBM-3086, KBE-585A, X-12-1048, X-12-50, X-12-5263HP, etc.

[0264] The silane coupling agent (L) may be a polymer type, such as a polysiloxane type or an organic polymer type.

[0265] The polysiloxane type is a compound in which the hydrolyzable group is 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 Chemical Co., Ltd.

[0266] The organic polymer type is a silane coupling agent (L) in which the hydrolyzable group is 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, and X-12-1159L manufactured by Shin-Etsu Chemical Co., Ltd.

[0267] The silane coupling agent (L) can be used alone or in combination of two or more kinds.

[0268] The content of the silane coupling agent (L) is preferably from 0.1 to 10 mass % in 100 mass % of the nonvolatile content of the photosensitive composition.

[0269] [Antioxidants (M)] The photosensitive composition of the present invention can contain an antioxidant (M).

[0270] The antioxidant (M) is not particularly limited, and known compounds can be used. For example, hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds can be mentioned. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0271] Examples of the hindered phenol antioxidant include 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 4,4'-butylidene-bis-(2-tert-butyl-5-methylphenol), 3-(3,5-di-tert-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di- tert-Butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamamide), iso-octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester salt, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid]ethylene bisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-trimethylanilino Azine, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-tert-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc.

[0272] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0273] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0274] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd., and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0275] Examples of phosphorus-based antioxidants include di(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidenedipheno tris(diphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(biphenyl) phosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexatridecyl 1,1,3-tri Examples of such phosphite include bis(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-tert-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-tert-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite.

[0276] Examples of commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0277] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0278] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0279] The antioxidants (M) can be used alone or in combination of two or more kinds.

[0280] The content of the antioxidant (M) is preferably from 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0281] [Leveling agent (N)] The photosensitive composition of the present invention can contain a leveling agent (N).

[0282] The leveling agent (N) is not particularly limited, and known compounds can be used. Examples of the leveling agent include silicone-based leveling agents, fluorine-based leveling agents, acrylic-based leveling agents, and acetylene diol-based leveling agents.

[0283] Examples of commercially available silicone leveling agents include 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.; FZ-7002, 2110, 2122, 2123, 2191, and 5609 manufactured by Toray Dow Corning Co., Ltd.; Examples of such products include 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 manufactured by Chemical Industry Co., Ltd.; TegoGlide 432, 440, and 450, TegoWet 250, 260, 265, 270, and 280 manufactured by Evonik Corporation; and MEGAFACE EFS-131, EFS-321, EFS-521, and EFS-801 manufactured by DIC Corporation.

[0284] Examples of commercially available fluorine-based leveling agents include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, and RS-72-K 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.

[0285] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, and 394 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0286] Commercially available acetylene diol leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0287] The leveling agent (N) can be used alone or in combination of two or more kinds.

[0288] The content of the leveling agent (N) is preferably from 0.001 to 2.0 mass %, and more preferably from 0.005 to 1.0 mass %, based on 100 mass % of the nonvolatile content of the photosensitive composition.

[0289] [Storage stabilizer (O)] The photosensitive composition of the present invention may contain a storage stabilizer (O).

[0290] The storage stabilizer (O) is not particularly limited, and known compounds can be used, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine and tetraphenyl, phosphites, etc.

[0291] The content of the storage stabilizer (O) is preferably from 0.05 to 5% by mass based on 100% by mass of the nonvolatile content of the photosensitive composition.

[0292] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0293] The organic solvent (P) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, 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-methyl Butyl acetate, 3-methoxy-1-butanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl benzene, 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.,

[0294] From the viewpoint of the environment, the photosensitive composition of the present invention preferably does not substantially contain organic solvents that are aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.) Substantially not containing means that the content of such organic solvents in the photosensitive composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less.

[0295] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0296] The content of the organic solvent (P) is preferably such that the nonvolatile content of the photosensitive composition is 5 to 60% by mass.

[0297] [Other components (Q)] The photosensitive composition of the present invention may contain components other than those described above (hereinafter, simply referred to as other components (Q)). Examples of other components (Q) include transparent particles, near-infrared ray absorbing compounds, surfactants, acid generators, salt generators, curing catalysts, etc. The content of the other components may be appropriately set within a range that does not impair the effects of the present invention.

[0298] [Specific metal element content] The 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.

[0299] A 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).

[0300] [Water content] The photosensitive composition of the present invention preferably has a water content of 2.0% by mass or less.

[0301] A 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.

[0302] [Method of producing photosensitive composition] The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive 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 (P) and then mixed successively. For example, a dispersion is produced by adding a color material (A), a dispersion resin (H), an organic solvent (P), etc., and carrying out a dispersion treatment. Then, a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), an ultraviolet absorber (E), etc. 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.

[0303] 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.

[0304] 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 photosensitive composition having high dispersion stability is easily obtained.

[0305] 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.

[0306] The photosensitive 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 photosensitive composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0307] The photosensitive composition of the present invention is preferably used for a white pixel in combination with any one of a red pixel, a green pixel, and a blue pixel, although the present invention is not limited thereto.

[0308] <Membrane> The film of the present invention is a film formed from the above-mentioned photosensitive composition. The film is preferably a patterned film, but may also be used as a flat film without forming a pattern.

[0309] [Membrane manufacturing method] The method for producing the film is not particularly limited, and any known method can be used. For example, the film can be produced through a step of applying the photosensitive composition of the present invention onto a substrate and a step of drying the composition.

[0310] [Coating process] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, or colored glass such as blue glass may be used depending on the application. Examples of the resin include polyester-based resins such as polyester terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonate resins, and epoxy resins. The thickness of the substrate is preferably 0.01 to 10 mm. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or a CMOS may be formed on the substrate. Also, an undercoat layer may be provided on the substrate as necessary to improve adhesion with the upper layer, prevent diffusion of substances, and flatten the surface.

[0311] The coating method is not particularly limited, and any known method can be used, 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, and offset printing.

[0312] 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.

[0313] [Drying process] The method for drying the film applied to the substrate is not particularly limited, and any known method can be used. For example, reduced pressure drying using a vacuum drying device, heat drying using a hot plate, an IR oven, a convection oven, or the like, and a combination of these methods can be used.

[0314] The drying temperature and time can be appropriately adjusted. The drying temperature is preferably about 50 to 130° C., and the drying time is preferably about 5 seconds to 5 minutes.

[0315] 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. Note that, when the film is used as a flat film, the step of forming a pattern is not necessary.

[0316] The method for forming the pattern will now be described in detail.

[0317] When a pattern is formed by a photolithography method, for example, the photosensitive composition of the present invention is applied onto a substrate, and the layer formed by drying is exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed with an alkaline developer (development step), and the pattern is then heat-treated (post-bake step).

[0318] [Exposure process] In the exposure process, the layer formed by coating and drying 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). When using light with a specific wavelength, an optical filter can also be used. 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.

[0319] [Development process] Next, an alkaline development process is carried out, whereby the unexposed portions of the layer are dissolved in an alkaline developer, and only the hardened portions remain, yielding a patterned film. Examples of the alkaline developer include aqueous solutions containing 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, 1,8-diazabicyclo-[5.4.0]-7-undecene, etc. Two or more of these alkaline compounds can be used in combination. The alkaline developer may contain a surfactant and an organic solvent in addition to the alkaline compound and water. 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.

[0320] [Post-bake process] After development, a heat treatment (post-baking) is performed, which improves the film's resistance. The temperature is preferably 80 to 300° C., more preferably 100 to 240° C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as the light-emitting layer is used, or from the viewpoint of the environment, the temperature is preferably 180° C. or less.

[0321] Next, the transmittance in each wavelength region of the film formed from the photosensitive composition of the present invention will be described.

[0322] [Transmittance at wavelengths of 380 to 480 nm] From the viewpoint of improving the brightness and sensitivity of RGB pixels, the photosensitive composition of the present invention, when formed into a film having a thickness of 2.0 μm, preferably has a transmittance of 87% or more, more preferably 90% or more, at a wavelength of 380 to 480 nm.

[0323] [Transmittance at wavelengths of 500 to 580 nm] From the viewpoint of suppressing reflection of external light, the photosensitive composition of the present invention, when formed into a film having a thickness of 2.0 μm, preferably has a maximum transmittance of 70 to 90%, more preferably 80 to 90%, at a wavelength of 500 to 580 nm.

[0324] [Transmittance at wavelengths of 600 to 780 nm] From the viewpoint of improving the brightness and sensitivity of RGB pixels, the photosensitive composition of the present invention, when formed into a film having a thickness of 2.0 μm, preferably has a transmittance of 93% or more, more preferably 95% or more, at a wavelength of 600 to 780 nm.

[0325] The methods for measuring the thickness and transmittance of the film are described below.

[0326] (Film thickness measurement) The photosensitive composition of the present invention was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after post-baking would be 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, an ultra-high pressure mercury lamp was used to apply the composition to the substrate through a photomask with a 100 μm square pattern at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was then 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, air-dried, and post-baked in a clean oven at 230°C for 30 minutes to form a square pattern on the substrate. The spray development was carried out for the shortest possible time for forming a pattern with no residual development for each film of the photosensitive composition. Then, using Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.), measurements were taken at five random locations, and the average value was taken as the film thickness. The thickness of 2.0 μm includes the range of error permitted in the technical field to which the present invention pertains, specifically, the thickness is within the range of 2.0 μm±0.07 μm.

[0327] (Transmittance measurement) The film thickness was then measured, and the transmittance in the thickness direction of the film at each wavelength was measured using OSP-SP100 (manufactured by Olympus Corporation).

[0328] <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.

[0329] The color filter of the present invention preferably comprises a white pixel formed from the photosensitive composition of the present invention, and one or more pixels selected from the group consisting of red pixels, green pixels, and blue pixels.

[0330] <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.

[0331] 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.

[0332] <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.

[0333] 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).

[0334] An image display device having a color filter of the present invention will be described below with reference to Fig. 1, but the present invention is not limited to this within the scope of the present invention. In addition, Fig. 1 shows only characteristic components in an enlarged manner in order to make the characteristics easier to understand, and each component and its dimensional ratio are not the same as the actual ones.

[0335] The image display device of Fig. 1 is formed by laminating a transparent substrate 100, a TFT array 200, a color filter layer 300, a resin layer 400, a protective layer 500, a transparent electrode 600, a WOLED 700, and a metal electrode 800 in this order. The color filter layer 300 is a four-color filter including a red pixel 300R, a green pixel 300G, a blue pixel 300B, and a white pixel 300W, and includes a black matrix 300BM at the boundary between the pixels. The white pixel 300W is formed using the photosensitive composition of the present invention. EXAMPLES

[0336] 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.

[0337] Before describing the examples, each measurement method will be described.

[0338] The weight average molecular weight (Mw), number average molecular weight (Mn), and acid value (mgKOH / g) were measured as follows.

[0339] (Molecular weight) Weight average molecular weight (Mw) and number average molecular weight (Mn) 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.

[0340] (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.

[0341] <Production of Colorant (A)> (Purple color material (A1-1)) 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 salt-forming resin 1. Next, 30 parts of salt-forming resin 1 in terms of non-volatile content was added to 2,000 parts of water, and the mixture was thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52, a compound having a xanthene skeleton, in 90 parts of water, and the solution was gradually added dropwise to the salt-forming resin 1 solution. After the dropwise addition, the mixture was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer after washing with water, to obtain a purple colorant (A1-1) which is a salt-forming compound of CI Acid Red 52, a compound having a xanthene skeleton, and salt-forming resin 1. At this time, the content of the colorant component derived from CI Acid Red 52 in the purple colorant (A1-1) was 25% by mass.

[0342] (Purple color material (A1-2)) A purple colorant (A1-2) was produced in the same manner as for the purple colorant (A1-1), except that CI Acid Red 52 was changed to CI Acid Red 289. At this time, the content of the colorant component derived from CI Acid Red 289 in the purple colorant (A1-2) was 25 mass%.

[0343] (Purple color material (A1-3)) 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 salt-forming resin 2. The weight average molecular weight was 7,700. Next, 30 parts of salt-forming 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 (11) 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 the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer after washing with water, to obtain a purple colorant (A1-3) which is a salt-forming compound of 32 parts of the compound represented by the chemical formula (11) and the salt-forming resin 2. At this time, the content of the colorant component derived from the compound represented by the chemical formula (11) in the purple colorant (A1-3) was 25% by mass.

[0344] Chemical formula (11) [ka]

[0345] <Production of binder resin (B)> (Solution of binder resin (B1-1) having thermal crosslinking group) In a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 4 parts of trimellitic anhydride, 2.0 parts of 3-mercapto-1,2-propanediol, 50.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc), and 0.1 parts of dimethylbenzylamine were charged. After replacing with nitrogen gas, the reaction vessel was heated to 120 ° C. and reacted for 4 hours, and then reacted at 80 ° C. for 2 hours. Furthermore, 30.0 parts of tert-butyl acrylate, 20.0 parts of methyl methacrylate (3-ethyloxetan-3-yl) (ETERNACOLL (registered trademark) OXMA manufactured by Ube Industries, Ltd.), 5.0 parts of methacrylic acid, 40.0 parts of ethyl acrylate, and 10.0 parts of PGMAc were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes while maintaining the reaction vessel at 80 ° C. One hour after the final addition, the non-volatile content was measured and it was confirmed that 95% or more had reacted. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, to prepare a binder resin (B1-1) solution having a thermal crosslinking group. The acid value was 55 mgKOH / g, and the weight average molecular weight was 15,000.

[0346] (Solution of binder resin (B1-2) having thermal crosslinking group) 100 parts of PGMAc was placed in 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 78°C. Next, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6A mixture of 17.6 parts of decan-9-yl acrylate (1:1 molar ratio), 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 each added dropwise from the dropping funnel into the flask. After the dropwise addition, the mixture was stirred at 78°C for 3 hours to react. After cooling, PGMAc was added so that the non-volatile content became 30% by mass, and a binder resin (B1-2) solution having a thermal crosslinking group was prepared. The acid value was 73 mgKOH / g, and the weight average molecular weight was 8,200.

[0347] (Solution of binder resin (B1-3) having thermal crosslinking 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 PGMAc, 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. After cooling, PGMAc was added so that the non-volatile content became 30% by mass, and a binder resin (B1-3) solution having a thermal crosslinking group was prepared. The acid value was 74 mgKOH / g, and the weight average molecular weight was 8,000.

[0348] (Other binder resin (B2-1) solutions) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was stirred while being replaced with nitrogen, and heated to 120°C. Next, a mixture of 76.8 parts of glycidyl methacrylate, 66.1 parts of dicyclopentanyl methacrylate, and 16.7 parts of styrene, and a mixture of 5.5 parts of azobisisobutyronitrile as a polymerization initiator dissolved in PGMAc, was dropped into the flask from the dropping funnel over 2.5 hours. After the dropwise addition was completed, the mixture was stirred at 120°C for another 2 hours. Next, the flask was replaced with air, and 38.9 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added as modified compounds, and reacted at 120°C for 5 hours. This caused all of the epoxy groups of glycidyl methacrylate to react with the carboxyl groups of acrylic acid. Next, 40.0 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted for 4 hours at 120° C. As a result, some of the hydroxyl groups generated by cleavage of the epoxy groups of glycidyl methacrylate reacted with succinic anhydride. After cooling, PGMAc was added so that the non-volatile content became 30% by mass, and another binder resin (B2-1) solution was prepared. The acid value was 95 mgKOH / g, and the weight average molecular weight was 9,000.

[0349] (Other binder resin (B2-2) solution) A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube was charged with 100 parts of PGMAc, which was stirred while replacing with nitrogen, and heated to 120°C. Next, a mixture of 109.25 parts of benzyl methacrylate, 24.1 parts of methacrylic acid, 22.03 parts of dicyclopentanyl methacrylate, 1.0 part of azobisisobutyronitrile as a polymerization initiator, and PGMAc was dropped into the flask from the dropping funnel over 2.5 hours. After the dropwise addition, the mixture was stirred at 120°C for another 2 hours to react. After cooling, PGMAc was added so that the non-volatile content became 30% by mass, and another binder resin (B2-2) solution was prepared. The acid value was 98 mgKOH / g, and the weight average molecular weight was 17,500.

[0350] [Polymerizable compound (C)] (Multifunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure (C1-1)) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air inlet tube, 634.7 parts of trimethylolpropane triacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually added dropwise from the dropping funnel into the flask to carry out a reaction. After the addition was completed, the reaction was continued with stirring at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropping was completed, the reaction was carried out at 100°C for 4 hours with stirring to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0351] (Multifunctional urethane (meth)acrylate (C1-2) having a secondary amine or tertiary amine structure) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air inlet tube, 998.4 parts of ditrimethylolpropane tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropwise addition, the reaction was continued with stirring at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropping was completed, the reaction was carried out at 100°C for 4 hours with stirring to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0352] (Multifunctional urethane (meth)acrylate (C1-3) having a secondary amine or tertiary amine structure) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropwise addition, the reaction was continued with stirring at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropping was completed, the reaction was carried out at 100°C for 4 hours with stirring to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0353] (Multifunctional urethane (meth)acrylate (C1-4) having a secondary amine or tertiary amine structure) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropwise addition, the reaction was continued with stirring at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 149.7 parts of hexamethylene diisocyanate was gradually dropped into the flask from the dropping funnel to carry out the reaction. After the dropping was completed, the reaction was carried out at 100°C for 4 hours with stirring, to obtain an aliphatic multifunctional urethane acrylate having a tertiary amine structure.

[0354] (Multifunctional urethane (meth)acrylates (C1-5) having a secondary amine or tertiary amine structure) In a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and an air inlet tube, 754.0 parts of pentaerythritol tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite and 2.0 parts of phenothiazine were placed, and the mixture was heated to 50°C while stirring. Next, 160.8 parts of N-methylethanolamine was gradually dropped into the flask from the dropping funnel to carry out a reaction. After the dropwise addition, the reaction was continued with stirring at 50°C for 2 hours. Next, the temperature was raised to 100°C, and 155.0 parts of 2,4-tolylene diisocyanate was gradually added dropwise from the dropping funnel into the flask to carry out the reaction. After the dropping was completed, the reaction was carried out at 100°C for 4 hours with stirring to obtain an aromatic polyfunctional urethane acrylate having a tertiary amine structure.

[0355] [Dispersion resin (H)] (Dispersed resin (H-1) solution) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10.0 parts of methacrylic acid, 100.0 parts of methyl methacrylate, 70.0 parts of iso-butyl methacrylate, 20.0 parts of benzyl methacrylate, and 50.0 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12.0 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 added to 90.0 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19.0 parts of pyromellitic anhydride, 50.0 parts of PGMAc, 50.0 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 for 7 hours at 100°C. The reaction was terminated when it was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified. After cooling, PGMAc was added so that the non-volatile content was 30% by mass, to obtain a dispersion resin (H-1) solution. The acid value was 70 mgKOH / g and the weight average molecular weight was 8,500.

[0356] <Preparation of Dispersion> (Purple dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan "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 purple dispersion 1. The non-volatile content was 25.0 mass%. Purple color material (A1-4): 15.0 parts Pigment derivative (G-1): 1.0 part Dispersion resin (H-1) solution: 30.0 parts Organic solvent (P-1): 54.0 parts

[0357] (Purple Dispersions 2 and 3, Blue Dispersions 1 and 2) Purple dispersions 2 and 3 and blue dispersions 1 and 2 were prepared in the same manner as for purple dispersion 1, except that the raw materials and amounts shown in Table 1 were changed.

[0358] [Table 1]

[0359] The components listed in Table 1 are as follows:

[0360] Colorant (Purple color material (A1)) A1-4: CI Pigment Violet 19 A1-5: CI Pigment Violet 23 A1-6: CI Pigment Violet 29

[0361] (Blue color material (A2)) A2-1: CI Pigment Blue 15:3 A2-2: CI Pigment Blue 15:6

[0362] The purple color material (A1) and the blue color material (A2) were both finely milled by salt milling, thoroughly washed with ion-exchanged water so as to have the above-mentioned specific metal contents, and then dried before use.

[0363] [Pigment derivatives (G)] [ka]

[0364] [Organic solvent (P)] P-1:PGMAc

[0365] <Production of Photosensitive Composition> [Example 1] (Photosensitive composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Composition 1. The nonvolatile content was 25.0% by mass. Purple coloring material (A1-2): 2.10 parts Purple dispersion 2: 0.90 parts Blue dispersion 2: 0.60 parts Binder resin (B1-1) solution having a thermal crosslinking group: 125.00 parts Other binder resin (B2-1) solution: 108.32 parts Multifunctional urethane (meth)acrylate (C1-6) having a secondary amine or tertiary amine structure: 7.50 parts Other (meth)acrylates (C2-1): 142.70 parts Compound (D1-1) represented by general formula (1): 10.00 parts Triazine compound (E1-1): 2.50 parts Triazine compound (E1-2): 2.00 parts Polymerization inhibitor (F-1): 0.13 parts Thermal crosslinkable compound (J-1): 12.50 parts Leveling agent (N-1): 0.20 parts Organic solvent (P): 585.55 parts

[0366] [Examples 2 to 43 and Comparative Examples 1 to 3] (Photosensitive composition 2-46) Photosensitive compositions 2 to 46 were prepared in the same manner as in Example 1, except that the composition of Example 1 was changed to the raw materials and amounts shown in Tables 2 to 6. In the tables, the binder resin (B1) solution having a thermal crosslinkable group is referred to as the binder resin (B1) solution. In addition, the value of "Amount of color material (A) in the non-volatile matter (%)" and the value of "Amount of purple color material (A1) in the color material (A) (%)" in the table were calculated by subtracting the amount of salt-forming resin from the quantities of the purple color materials (A1-1) to (A1-3) in the table, and using the amount of purple color material (A1) as the value.

[0367] [Table 2]

[0368] [Table 3]

[0369] [Table 4]

[0370] [Table 5]

[0371] [Table 6]

[0372] The respective raw materials listed in Tables 2 to 6 are as follows.

[0373] [Polymerizable compound (C)] (Multifunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure) C1-6: CN9906NS (Arkema, aliphatic multifunctional urethane acrylate with a tertiary amine structure of Mw 13,200 and Mn 3,900)

[0374] (Other (Meta)Acrylates (C2)) C2-1: Aronix M-450 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) C2-2: Aronix M-510 (manufactured by Toagosei Co., Ltd., a trifunctional acrylate with an acidic group) C2-3: Aronix M-315 (manufactured by Toagosei Co., Ltd., a mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate)

[0375] [Polymerization initiator (D)] (Compound (D1) represented by general formula (1)) D1-1: The above-mentioned compound (D1-1) D1-2: The above-mentioned compound (D1-2) D1-3: The above-mentioned compound (D1-3) D1-4: The above-mentioned compound (D1-4)

[0376] (Other polymerization initiators (D2)) D2-1: Omnirad369E (IGM Resins, α-aminoketone compound) D2-2: Omnirad907 (IGM Resins, α-aminoketone compound) D2-3: Irgacure OXE-02 (BASF Japan, oxime ester compound)

[0377] [Ultraviolet absorber (E)] (Triazine compound (E1)) E1-1: The above-mentioned compound (E1-1) E1-2: The above-mentioned compound (E1-2) E1-3: The above-mentioned compound (E1-3)

[0378] (Benzotriazole compound (E2)) E2-1: The above-mentioned compound (E2-1)

[0379] (Benzophenone compounds (E3)) E3-1: The above-mentioned compound (E3-1)

[0380] [Polymerization inhibitor (F)] F-1: Methylhydroquinone F-2: p-Methoxyphenol

[0381] [Thermal crosslinkable compound (J)] J-1: EHPE-3150 (manufactured by Daicel Corporation, a compound represented by general formula (10), with an average of 15 epoxy groups and an epoxy equivalent of 170 to 190 g / eq)

[0382] [Leveling agent (N)] N-1: A mixture of BYK-330 (manufactured by BYK-Chemie, polyether-modified dimethylsiloxane) and a block copolymer having the following structure (n:m = 50:50 (mol%)) in a mass ratio of 8:2

[0383] [ka]

[0384] [Organic solvent (P)] P-1:PGMAc P-2: Propylene glycol monomethyl ether P-3: 3-Methoxy-1-butanol P-4: Ethyl 3-ethoxypropionate The above P-1, P-2, P-3, and P-4 were mixed in a mass ratio of 80:10:5:5 to prepare an organic solvent (P).

[0385] <Evaluation of Photosensitive Composition> The following evaluations were carried out on the obtained photosensitive compositions 1 to 46. The evaluation results are shown in Table 7.

[0386] [Pattern Formation Evaluation: (1) Line Width] The obtained 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 2.0 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 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 substrate was post-baked in a clean oven at 230° C. for 30 minutes. The spray development was performed for the shortest time possible to form a pattern without leaving any residual development for the coating of each photosensitive composition, and this was determined as the appropriate development time. 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

[0387] [Pattern Formability Evaluation: (2) Cross-sectional Shape] The obtained 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 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask having a 100 μm-wide stripe pattern at an illumination intensity of 30 mW / cm. 2 , exposure dose 50mJ / cm 2 The substrate was then 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, air-dried, and post-baked in a clean oven at 230° C. for 30 minutes. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development for the coating of each photosensitive composition, and this was determined as the appropriate development time. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope (Hitachi High-Tech Corporation "S-3000H"). For evaluation, SEM images of the cross section of a 100 μm wide stripe pattern were captured, and the taper angle between the substrate and the end of the pattern cross section was measured. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Taper angle is 40 degrees or more, but less than 50 degrees 4: Taper angle is 30 degrees or more, but less than 40 degrees 3: Taper angle is 20 degrees or more and less than 30 degrees 2: Taper angle is 10 degrees or more, less than 20 degrees, or 50 degrees or more 1: Taper angle less than 10 degrees

[0388] [Pattern Formation Evaluation: (3) Adhesion] The obtained 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 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern of widths of 5 μm, 10 μm, 15 μm, 20 μm, and 25 μm at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2The substrate was then 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, air-dried, and post-baked in a clean oven at 230°C for 30 minutes. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development for each photosensitive composition coating, and this was determined as the appropriate development time. The patterns of 5 to 25 μm in width on the evaluation substrate were observed with an optical microscope to confirm the remaining patterns. The evaluation criteria are as follows, with 3 or more being considered practical. 5: Patterns of 10 μm or less remain. 4: Patterns of 15 μm or more remain. Patterns of 10 μm or less do not remain. 3: Patterns of 20 μm or more remain. Patterns of 15 μm or less do not remain. 2: 25μm pattern remains. No pattern of 20μm or less remains. 1: No pattern remains.

[0389] [Pattern Formation Evaluation: (4) Plane Smoothness] The obtained resin 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 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a square pattern of 20 μm squares at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was then 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, air-dried, and post-baked in a clean oven at 230°C for 30 minutes. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development for each photosensitive composition coating, and this was determined as the appropriate development time. The film thickness was measured using an optical film thickness meter (F50) manufactured by Filmetrics. The evaluation was performed by calculating the difference in film thickness between the thinnest part and the thickest part (hereinafter referred to as film thickness difference). The evaluation criteria are as follows, with 3 or more being practical. 5: Film thickness difference is 0.02 μm or less 4: The difference in thickness is greater than 0.02 μm and less than 0.03 μm 3: The difference in thickness is greater than 0.03 μm and less than 0.04 μm 2: The difference in thickness is greater than 0.04 μm and less than 0.05 μm 1: The thickness difference is greater than 0.05 μm

[0390] <Preparation of substrate for transmittance evaluation> The obtained resin 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 post-baked film thickness was 2.0 μm, and then dried on a hot plate at 90° C. for 2 minutes. Next, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to illuminate the substrate through a photomask with a 100 μm square pattern at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was then exposed to ultraviolet light at 23° C. Thereafter, 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, air-dried, and post-baked in a clean oven at 230° C. for 30 minutes. The spray development was carried out for the shortest time possible for forming a pattern without leaving any residual development for the coating of each photosensitive composition, and this was determined as the appropriate development time.

[0391] [Transmittance at wavelengths of 380 to 480 nm] The obtained substrate for transmittance evaluation was measured for transmittance at wavelengths of 380 to 480 nm in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation.) The evaluation criteria are as follows, with 2 or more being practical. 3: Transmittance is 90% or more at wavelengths of 380 to 480 nm 2: Transmittance is 87% or more and less than 90% at wavelengths of 380 to 480 nm 1: There are areas with transmittance of less than 87% at wavelengths between 380 and 480 nm

[0392] [Transmittance at wavelengths of 500 to 580 nm] The obtained substrate for transmittance evaluation was measured for transmittance at wavelengths of 500 to 580 nm in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation.) The evaluation criteria are as follows, with 2 or more being practical. 3: The maximum transmittance is 80% or more and 90% or less at wavelengths of 500 to 580 nm. 2: The maximum transmittance is 70% or more and less than 80% at a wavelength of 500 to 580 nm. 1: Maximum transmittance is less than 70% or more than 90% at wavelengths of 500 to 580 nm

[0393] [Transmittance at wavelengths of 600 to 780 nm] The obtained substrate for transmittance evaluation was measured for transmittance at wavelengths of 600 to 780 nm in the thickness direction of the coating using OSP-SP100 (manufactured by Olympus Corporation.) The evaluation criteria are as follows, with 2 or more being practical. 3: Transmittance is 95% or more at wavelengths of 600 to 780 nm 2: Transmittance is 93% or more and less than 95% at wavelengths of 600 to 780 nm 1: There are areas with transmittance of less than 93% at wavelengths between 600 and 780 nm

[0394] [Table 7]

[0395] As is clear from the comparison of Examples 1 to 43 and Comparative Examples 1 and 2 in Table 7, by setting the content of color material (A) in 100% by mass of the nonvolatile content of the photosensitive composition to 1% by mass or less and the content of purple color material (A1) in 100% by mass of color material (A) to 50% by mass or more, it is possible to achieve a transmittance of 87% or more at wavelengths of 380 to 480 nm, a maximum transmittance of 70 to 90% at wavelengths of 500 to 580 nm, and a transmittance of 93% or more at wavelengths of 600 to 780 nm. This makes it possible to form white pixels that can absorb, for example, green light emitted from a WOLED and suppress reflection of external light. [Explanation of symbols]

[0396] 100 Transparent substrate 200 TFT array 300 Color filter layer (300R: red pixel, 300G: green pixel, 300B: blue pixel, 300W: white pixel, 300BM: black matrix) 400 resin layer 500 protective layer 600 transparent electrode 700 WOLED 800 metal electrode

Claims

1. A photosensitive composition comprising a colorant (A), a binder resin (B), a polymerizable compound (C), a polymerization initiator (D), and an ultraviolet absorber (E), the content of the color material (A) is 1 mass% or less based on 100 mass% of the nonvolatile content of the photosensitive composition, the color material (A) contains a purple color material (A1), and the content of the purple color material (A1) is 50% by mass or more in 100% by mass of the color material (A); The photosensitive composition, wherein the polymerization initiator (D) is substantially free of an oxime ester compound.

2. The photosensitive composition according to claim 1 , wherein the polymerizable compound (C) comprises a polyfunctional urethane (meth)acrylate (C1) having a secondary amine or tertiary amine structure.

3. The photosensitive composition according to claim 1 , wherein the polymerization initiator (D) comprises a compound (D1) represented by the following general formula (1): General formula (1) 【Chemistry 20】 (In general formula (1), R １ and R ２ R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ represents a hydrogen atom or a monovalent substituent.

4. The photosensitive composition according to claim 1 , wherein the binder resin (B) comprises a binder resin (B1) having a thermally crosslinkable group.

5. The photosensitive composition according to claim 1, wherein the purple colorant (A1) comprises at least one selected from the group consisting of C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, and a compound having a xanthene skeleton.

6. The photosensitive composition according to claim 1 , further comprising a polymerization inhibitor (F).

7. A film formed from the photosensitive composition according to any one of claims 1 to 6.

8. A color filter comprising the film according to claim 7.

9. A solid-state imaging device comprising the color filter according to claim 8.

10. An image display device comprising the color filter according to claim 8.

Images