WO2021014956A1 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

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Publication number
WO2021014956A1
WO2021014956A1 PCT/JP2020/026436 JP2020026436W WO2021014956A1 WO 2021014956 A1 WO2021014956 A1 WO 2021014956A1 JP 2020026436 W JP2020026436 W JP 2020026436W WO 2021014956 A1 WO2021014956 A1 WO 2021014956A1
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Prior art keywords
group
photosensitive resin
resin composition
bank
component
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PCT/JP2020/026436
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French (fr)
Japanese (ja)
Inventor
佳代 稲見
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日産化学株式会社
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Application filed by 日産化学株式会社 filed Critical 日産化学株式会社
Priority to KR1020227001949A priority Critical patent/KR20220039710A/en
Priority to JP2021533917A priority patent/JPWO2021014956A1/ja
Priority to CN202080052853.3A priority patent/CN114245881A/en
Publication of WO2021014956A1 publication Critical patent/WO2021014956A1/en

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers

Definitions

  • the present invention relates to a photosensitive resin composition and a cured film obtained from the photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high liquid repellency on the surface of a cured film, a cured film thereof, and various materials using the cured film.
  • This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light-shielding material compatible with an inkjet method, or a partition material.
  • Patent Document 2 proposes to prevent uneven film thickness by partitioning pixels by using a plurality of partition walls and ink flow prevention plate members arranged in parallel (Patent Document 2). ). Further, it has been proposed that by adopting two types of banks that intersect in a grid pattern, the occurrence of color mixing during ink application is suppressed, and display with high color purity becomes possible (Patent Document 3). However, when the ink is applied onto the partition wall or the plate member, the ink may aggregate on the partition wall or the plate member or the pixel electrode.
  • the present invention has been made in view of the above circumstances, and the problem to be solved is that it is used for a liquid crystal display element, an organic electroluminescence element, etc., and the photosensitive resin composition of the present invention provides a high base solution.
  • An object of the present invention is to provide a cured film having a property, and a cured film that suppresses coating unevenness of the upper layer material laminated by using an inkjet method, a slit coating method, or the like.
  • the present invention relates to the following.
  • 1. A composition that is applied as a material for the first bank in a display device in which individual pixel areas are defined by arranging the first bank and the second bank directly on the substrate or via another layer.
  • a photosensitive resin composition containing the following components (A), (B), (C) and (D).
  • C) component solvent
  • D photosensitizer 2.
  • the first bank has a structure arranged adjacent to the second bank and / or a structure isolated in an area surrounded by the second bank, and / or the first bank.
  • the photosensitive resin composition according to item 1 wherein the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface. 3.
  • the second bank forms a structure arranged directly above the first bank or via another layer.
  • the fluorine-containing pyrolytic polymer, which is the component (B) has a main chain (a) having a polymer structure of a polymerizable monomer and a side chain having a functional group represented by the following general formula (1).
  • the photosensitive resin composition according to any one of the above items 1 to 3 which is a fluorine-containing pyrolytic polymer having (b).
  • R 1 , R 2 and R 3 are independently hydrogen atoms or organic groups having 1 to 18 carbon atoms, and R 4 is a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain. .
  • Y 1 is an oxygen atom or a sulfur atom.
  • R4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded. 6.
  • the photosensitive resin composition according to any one of the above items 1 to 4 wherein R4 is a fluorinated alkyl group having 4 to 6 carbon atoms to which a fluorine atom is directly bonded. 7. Items 1 to 2 above, wherein R 1 , R 2 and R 3 are independent hydrogen atoms, and R 4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded.
  • the photosensitive resin composition according to any one of the above items 1 to 8, which satisfies at least one of the following (Z1) to (Z4).
  • (Z2): The alkali-soluble resin further has a self-crosslinking group or is a group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Further having a group that reacts with at least one group selected from (Z3):
  • the photosensitive agent is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as the component (F).
  • the photosensitizer is a photoacid generator, and further contains, as a component (G), a compound having two or more functional groups forming a covalent bond with the acid generated by the photoacid generator.
  • the photosensitive resin composition according to any one of the above items 1 to 9, wherein the photosensitizer is a quinonediazide compound.
  • the photosensitive resin composition according to any one of the above items 1 to 13 which contains 0.01 part by mass to 1 part by mass of the fluorine-containing pyrolytic polymer with respect to 100 parts by mass of the alkali-soluble resin. Stuff.
  • Photosensitive resin composition 17.
  • the first bank is a method for manufacturing a display element in which individual pixel regions are defined, which comprises the photosensitive resin composition according to any one of the above items 1 to 17.
  • the photosensitive resin composition of the present invention exhibits high liquidity.
  • the cured film formed by the photosensitive resin composition of the present invention has high wettability of the upper layer material laminated by using an inkjet method, a slit coating method, or the like while exhibiting high liquid-forming property, and suppresses coating unevenness. can do.
  • the ink does not aggregate on the partition wall and the plate member or the pixel electrode when the ink is applied, so that the occurrence of color mixing is suppressed and the display with high color purity is possible. is there.
  • FIG. 1 is a perspective view of the structure 100 in which the first bank and the second bank are formed.
  • FIG. 2 is a cross-sectional view of the AA'cut surface of the structure 100 in FIG.
  • FIG. 3 is a perspective view of the structure 200 in which the first bank and the second bank are formed.
  • 4A and 4B are cross-sectional views of the structure 200 in FIG. 3
  • FIG. 4A is a cross-sectional view of a BB'cut surface in FIG. 3
  • FIG. 4B is a schematic diagram of a CC'cut surface in FIG. Cross-sectional view.
  • FIG. 5 is a plan view showing the arrangement of the first bank and the second bank as a modification
  • FIG. 5A shows a modification showing a change in height of the first bank from the substrate surface
  • FIG. 5B shows a modification. Based on (a), a modified example in which the change in height from the substrate surface of the first bank becomes more complicated is shown.
  • the component (A) of the present invention is an alkali-soluble resin.
  • the resin contains an alkali-soluble group to impart alkali solubility, and examples of the alkali-soluble group include phenolic hydroxy group, carboxyl group, acid anhydride group, imide group, sulfonyl group, phosphoric acid, boric acid and activity. Examples include a methylene group and an active methine group.
  • the active methylene group refers to a methylene group (-CH 2- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophile.
  • the active methine group refers to an active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and having reactivity with a nucleophile.
  • the active methylene group is preferable, and the active methylene group represented by the following formula (a1) is more preferable.
  • R represents an alkyl group, an alkoxy group or a phenyl group, and the broken line represents a bond.
  • examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferable.
  • examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and the like. Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.
  • examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
  • examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and the like.
  • a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.
  • Examples of the group represented by the above formula (a1) include the following structures and the like.
  • the broken line represents the bond.
  • an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable to have.
  • the alkali-soluble resin of the component (A) may be any alkali-soluble resin having such a structure, and the type of the main chain skeleton and side chains of the polymer constituting the resin is not particularly limited.
  • the alkali-soluble resin of the component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is more than 50,000 and is excessive, development residue is likely to be generated and the sensitivity is greatly lowered, while if the number average molecular weight is less than 2,000 and is too small, the development is carried out. At that time, a considerable amount of film loss may occur in the exposed area, resulting in insufficient curing.
  • alkali-soluble resin of the component (A) examples include an acrylic resin, a polyhydroxystyrene resin, a polyimide precursor, and a polyimide.
  • an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (A).
  • the alkali-soluble resin of the component (A) may be a blend of a plurality of specific copolymers.
  • the above-mentioned specific copolymer consists of a monomer that expresses alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed by using at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.
  • the above-mentioned "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group” includes a monomer having a phenolic hydroxy group and a monomer having a carboxyl group. These monomers are not limited to those having one phenolic hydroxy group or carboxyl group, and may have a plurality of these monomers.
  • Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl).
  • Maleimide N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
  • Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.
  • the ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxy group and the polymerizable unsaturated group in the production of the alkali-soluble resin of the component (A) is all used in the production of the alkali-soluble resin of the component (A).
  • the monomers it is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, and most preferably 10 mol% to 30 mol%.
  • the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.
  • the alkali-soluble resin which is the component (A) of the present invention is obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing. Is preferable.
  • Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 2-hydroxyethyl methacrylate.
  • Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like.
  • the ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of the component (A) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, most preferably. It is preferably 20% by mass to 40% by mass. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by mass or more, the alkali-soluble group of the component (A) may be insufficient, and the properties such as developability may be deteriorated.
  • the alkali-soluble resin as the component (A) of the present invention is preferably a copolymer of an N-substituted maleimide compound from the viewpoint of raising the glass transition temperature (hereinafter referred to as Tg) of the copolymer.
  • N-substituted maleimide compound examples include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferable, those having an alicyclic skeleton are more preferable from the viewpoint of developability, transparency and heat resistance, and cyclohexylmaleimide is most preferable.
  • the ratio of the N-substituted maleimide in the production of the alkali-soluble resin of the component (A) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. Is.
  • the N-substituted maleimide is less than 5% by mass, the Tg of the copolymer becomes low, and the heat resistance may be inferior. If it is 60% by mass or more, the transparency may decrease.
  • the alkali-soluble resin of the component (A) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, or an amide. It is preferably a copolymer further having a group (hereinafter, also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a group and an amino group.
  • Examples of the self-crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group.
  • crosslinkable group examples include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group and the like.
  • the content is 0.1 to 0.9 per repeating unit in the resin of the component (A). It is preferable, and from the viewpoint of developability and solvent resistance, 0.1 to 0.8 is more preferable.
  • the alkali-soluble resin of the component (A) further includes self-crosslinking groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group, and N-alkoxymethyl.
  • self-crosslinking groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group, and N-alkoxymethyl.
  • a crosslinkable group such as a group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group
  • it has radical polymerizable property and is epoxy.
  • a crosslinkable group such as a group, an oxetane group, a vinyl group and a blocked isocyanate group
  • a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group. It may be copolymerized.
  • Examples of unsaturated compounds having radical polymerizable properties and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. And so on.
  • Examples of the monomer having radical polymerizable property and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
  • Examples of the monomer having radical polymerization property and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.
  • Examples of unsaturated compounds having radical polymerizable properties and having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, and ⁇ -n-butylacrylic acid.
  • Glycidyl acrylate-3,4-epoxybutyl, methacrylate-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylate-6,7-epoxyheptyl, ⁇ -ethylacrylic acid-6, Examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate.
  • glycidyl methacrylate -6,7-epoxyheptyl methacrylate
  • o-vinylbenzyl glycidyl ether o-vinylbenzyl glycidyl ether
  • m-vinylbenzyl glycidyl ether p-vinylbenzyl glycidyl ether
  • 3,4-epoxycyclohexyl methacrylate preferably used. These may be used alone or in combination.
  • Examples of the unsaturated compound having a radical polymerizable property and further having an oxetane group include a (meth) acrylic acid ester having an oxetane group.
  • a (meth) acrylic acid ester having an oxetane group examples include a (meth) acrylic acid ester having an oxetane group.
  • monomers 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl)- 3-Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxe
  • Examples of the monomer having radical polymerization property and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate and the like.
  • Examples of the monomer having a radical polymerizable property and a blocked isocyanate group include 2- (0- (1'-methylpropyridaneamino) carboxyamino) ethyl methacrylate and 2- (3,5-dimethylpyrazolyl) methacrylate. Carbonylamino) ethyl and the like can be mentioned.
  • the photosensitive resin composition of the present invention When the photosensitive resin composition of the present invention satisfies (Z2), it has radical polymerizable properties, and has N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and block.
  • the constituent units derived from the saturated compound are preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all the repeating units of the alkali-soluble resin of the component (A). contains. When this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while when the amount of this structural unit exceeds 70% by mass, the photosensitive resin composition is stable in storage
  • the acrylic polymer of the component (A) may be a copolymer formed by a monomer other than the above-mentioned monomer (hereinafter, referred to as other monomer) as a constituent unit.
  • the other monomer may be a monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and the monomer having a phenolic hydroxy group, and has the characteristics of the component (A). It is not particularly limited as long as it does not impair.
  • Such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds and the like. Specific examples of the other monomers will be given below, but the present invention is not limited thereto.
  • acrylic acid ester compound examples include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-.
  • methacrylic acid ester compound examples include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-.
  • acrylamide compound examples include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples thereof include methyl acrylamide and N-butoxymethylmethacrylamide.
  • vinyl compound examples include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2. -Epoxy-5-hexene, 1,7-octadiene monoepoxyside and the like.
  • styrene compound examples include styrene having no hydroxy group, for example, styrene, ⁇ -methylstyrene, chlorostyrene, bromostyrene and the like.
  • the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less. If it is more than 80% by mass, the essential components are relatively reduced, so that it becomes difficult to sufficiently obtain the effect of the present invention.
  • the method for obtaining the alkali-soluble resin which is the component (A) used in the present invention is not particularly limited, but for example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group are generated by the action of heat or acid.
  • the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvent described in the component (C) described later.
  • the acrylic polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.
  • the solution of the specific copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure.
  • the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
  • the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the component (C) described later and used as a solution.
  • a polyimide precursor such as a polyamic acid, a polyamic acid ester, a partially imidized polyamic acid, or a polyimide such as a carboxylic acid group-containing polyimide can be used, and these are alkali.
  • the type can be used without particular limitation.
  • the polyamic acid which is a polyimide precursor, can generally be obtained by polycondensing (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.
  • tetracarboxylic dianhydride compound is not particularly limited, and as specific examples, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3'.
  • 4,4'-benzophenonetetracarboxylic dianhydride 3,3', 4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride
  • aromatic tetracarboxylic acids 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Alicyclic tetracarboxylic dianhydride, 1,2,3, such as carboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalen
  • the diamine compound (j) is also not particularly limited, and for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1.
  • the compounding ratio of both compounds that is, (j) the total number of moles of the diamine compound / (i).
  • the total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced and the higher the molecular weight.
  • the carboxylic acid anhydride can be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group.
  • carboxylic acid anhydrides are phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydride phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid.
  • Anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.
  • the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
  • a reaction temperature of 5 ° C. to 40 ° C. and a reaction time of 1 hour to 48 hours are appropriately selected.
  • the reaction temperature can be selected from ⁇ 20 ° C. to 150 ° C., preferably ⁇ 5 ° C. to 100 ° C.
  • the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent.
  • Solvents that can be used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, etc.
  • the solution containing the polyamic acid thus obtained can be used as it is for the preparation of the photosensitive resin composition. Further, the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol or ethanol.
  • any polyimide can be used as the component (A).
  • the polyimide used in the present invention is a polyimide precursor such as the polyamic acid chemically or thermally imidized by 50% or more.
  • the polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
  • the method for introducing a carboxyl group or a phenolic hydroxy group into the polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing the amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, and a method.
  • a method of reducing the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamic acid is used.
  • Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
  • a method of chemical imidization a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is generally used.
  • thermal imidization a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 ° C. to 250 ° C. is generally used.
  • a phenol novolac resin can be further used as the alkali-soluble resin of the component (A).
  • polyester polycarboxylic acid can also be used as the alkali-soluble resin of the component (A).
  • Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO2009 / 051186.
  • the acid dianhydride include the above-mentioned (i) tetracarboxylic dianhydride.
  • the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F.
  • 1,4-Cyclohexanediol 1,3-Cyclohexanedimethanol
  • alicyclic diols such as 1,4-cyclohexanedimethanol
  • ethylene glycol propylene glycol
  • 1,4-butanediol 1,6-hexanediol
  • aliphatic diols and the like 1,4-Cyclohexanediol, 1,3-Cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And the like.
  • the alkali-soluble resin of the component (A) may be a mixture of a plurality of types of alkali-soluble resins.
  • the component (B) of the present invention is a fluorine-containing pyrolytic polymer.
  • the fluorine-containing thermally decomposable polymer has a main chain (a) having a thermally decomposable property and a polymer structure of a polymerizable monomer, and a side chain having a functional group represented by the general formula (1). It is characterized by having (b).
  • thermally decomposable means that it is thermally decomposed by being exposed to any environment of 50 to 300 ° C. for 30 minutes.
  • the structure blocking the carboxyl group is removed by exposing it to an environment of 50 to 300 ° C. for 30 minutes, and a carboxyl group is generated. ..
  • the fluorine-containing pyrolytic polymer of the component (B) include a main chain having a polymer structure of a polymerizable monomer and a side having an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain. Examples thereof include a chain and a side chain having a group having a structure represented by the general formula (1).
  • R 1 , R 2 and R 3 are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively. Further, it is preferable that R 1 , R 2 and R 3 are hydrogen atoms, respectively.
  • Y 1 is an oxygen atom or a sulfur atom.
  • R 4 is a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain.
  • a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom is preferable because a fluorine-containing thermally decomposable polymer exhibiting excellent smoothness can be obtained, and the fluorine atom is directly bonded.
  • a fluorinated alkyl group having 4 to 6 carbon atoms is more preferable, and a fluorinated alkyl group having 6 carbon atoms to which a fluorine atom is directly bonded is further preferable.
  • the R 4 represents, for example, any one group of the following formulas (Rf-1) to (Rf-7).
  • N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6.
  • m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23.
  • m is an integer of 1 to 5
  • n is an integer of 0 to 4
  • the sum of m and n is 4 to 5.
  • m is, for example, an integer of 1 to 6
  • n is an integer of 1 to 3
  • l is an integer of 1 to 20
  • p is an integer of 0 to 5.
  • the total product of m, p and n and l is 2 to 71.
  • m is an integer of 1 to 3
  • n is an integer of 1 to 3
  • l is an integer of 1 to 6
  • p is an integer of 0 to 2
  • m, p and n The sum of the products of and l is 2 to 23.
  • the formula (Rf-6) represents that R 4 is a poly (perfluoroalkylene ether) chain.
  • R 4 for example, the following formula ( ⁇ 1-1) can be preferably exemplified ⁇ ( ⁇ 1-4) or the like.
  • N in the formulas ( ⁇ 1-1) to ( ⁇ 1-3) is, for example, 0 to 5. Further, n in the formula ( ⁇ 1-4) is, for example, 0 to 20.
  • the side chain shown below can be preferably exemplified.
  • the one represented by the formula (1-1) is obtained by using an industrially available raw material, and has a low surface free energy, so that it exhibits excellent smoothness. It is preferable because the coalescence is easy to synthesize.
  • the fluorine-containing pyrolytic polymer of the present invention may contain a side chain (b') other than the general formula (1) as long as the effect of the present invention is not impaired.
  • a side chain represented by the following general formula (1') can be exemplified.
  • R 11 , R 21 and R 31 are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, R 41 is an organic group having 1 to 18 carbon atoms, and R 31 and R 41 are paired with each other. It may be bonded to to form a heterocycle having Y 11 as a hetero atom, and Y 11 is an oxygen atom or a sulfur atom.
  • R 11 , R 21 and R 31 are hydrogen atoms, respectively, and R 41 is an organic group having 1 to 18 carbon atoms.
  • a resist film in which Y 1 is an oxygen atom or a sulfur atom has a large difference in polarity between the blocked carboxyl group and the revived carboxyl group, and can achieve both smoothness and recoatability of the coating film. It is preferable because a fluorine-containing thermally decomposable polymer that can obtain a cured coating film such as a color filter protective film is obtained, and a side chain represented by the following formula (1'-1) is more preferable.
  • the fluorine-containing pyrolytic polymer a commercially available one may be used, and a main chain having a polymer structure of a polymerizable monomer and an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain are used.
  • DS-21 manufactured by DIC Co., Ltd.
  • DIC Co., Ltd. can be mentioned as an example having a side chain having a side chain and a side chain having a group having a structure represented by the general formula (1).
  • the fluorine-containing pyrolytic polymer is preferably contained in an amount of 0.01 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the alkali-soluble resin. ..
  • the component (C) used in the present invention dissolves the component (A), the component (B), and if necessary, the components (D) and (E) described below as a solvent, and is added as desired.
  • the type and structure of the solvent are not particularly limited as long as the solvent dissolves other additives and the like and has such a dissolving ability.
  • component (C) examples include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol.
  • solvents having no hydroxy group from the viewpoint of not dissolving the lower layer film, that is, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, Cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, ⁇ -butyrolactone, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, buty
  • solvents are generally used as solvents for photoresist materials.
  • a solvent having a hydroxy group it is preferable to use it in combination with a solvent having no hydroxy group from the viewpoint of not dissolving the lower layer film as described above.
  • the solvent to be combined is not particularly limited to one type or two or more types as long as the coating film property is good and the underlying film is not dissolved.
  • the amount of the solvent having a hydroxy group is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and 30% by weight, based on the whole component (C) from the viewpoint of not dissolving the underlayer film. Most preferably, it is by weight or less.
  • Examples of the photosensitizer as the component (D) include (D-1) 1,2-quinonediazide compound, (D-2) photoradical generator, and (D-3) photoacid generator.
  • the 1,2-quinonediazide compound is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, and these hydroxy groups or amino groups (with a hydroxy group). Of the total amount of both amino groups, preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol%, esterified with 1,2-quinonediazide sulfonic acid, or Amidated compounds can be used.
  • 1,2-quinone diazido sulfonic acid examples include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-.
  • examples thereof include diazido-4-sulfonic acid, and the chloride of 1,2-quinonediazide sulfonic acid can be used in the reaction with the above-mentioned compound having either one or both of a hydroxy group and an amino group.
  • Diazonaphthoquinone can be used as the (D-1) 1,2-quinone diazide compound.
  • Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallicate, ethyl gallicate, and 1,3,3-tris (4-hydroxyphenyl).
  • amino group-containing compound examples include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
  • aniline aniline
  • o-toluidine m-toluidine
  • p-toluidine 4-aminodiphenylmethane
  • 4-aminodiphenyl 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine.
  • 4,4'-Diaminophenylmethane, 4,4'-diaminodiphenyl ether, and other anilines aminocyclohexane can be mentioned.
  • examples of the compound containing both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol.
  • 1,2-quinonediazide compounds can be used alone or in combination of two or more.
  • the photosensitive resin composition of the present invention is a positive photosensitive resin composition
  • the contents when the compound having a quinonediazide group of the component (D-1) is contained are the component (A) and the component (B). It is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, and further preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass in total. If it is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developing solution becomes small, and patterning by development may be difficult.
  • the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or the component (D-1) absorbs light and the cured film. It may reduce transparency.
  • the photoradical generator is not particularly limited as long as it generates radicals by exposure.
  • Specific examples include the same components as (D-2) mentioned in the component (D) used in the above-mentioned composition for forming an upper layer film.
  • Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene, benzoin methyl ether, and benzoin ethyl.
  • Benzoin ethers such as ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-Triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4) -Mophorinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, 2-t
  • the above photoradical generator is easily available as a commercially available product, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, and IRGACURE 819.
  • IRGACURE 1880 IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE03, IRGACURE OXE03, IRGACURE OXE04, IRGACURE04 KAYACURE 2-EAQ (all manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ- 113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.) and the like can be mentioned. It is possible to use these photoradical generators alone or to use two or more of them in combination.
  • the content thereof is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). It is preferably 0.5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, the transmittance of the coating film may decrease or development failure of the unexposed portion may occur.
  • the photoacid generator of (D-3) is not particularly limited as long as it is a compound that photodecomposes to generate an acid when irradiated with ultraviolet rays.
  • Examples of the acid generated when the photoacid generator is photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-.
  • Toluene sulfonic acid campha sulfonic acid, trifluoromethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylen sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid and other sulfonic acids Examples thereof include acid or its hydrate and salt.
  • the photoacid generator examples include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. , And a cyano group-containing oxime sulfonate compound and the like.
  • Any of the conventionally known or conventionally used photoacid generators can be applied in the present invention without particular limitation.
  • the photoacid generator of the component (D) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].
  • the content thereof is preferably 0.01 mass by mass with respect to 100 parts by mass of the total of the components (A) and (B). Parts to 20 parts by mass, more preferably 0.1 parts to 10 parts by mass, still more preferably 0.5 parts to 8 parts by mass.
  • the content of the component (D-3) is 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted.
  • the amount is more than 20 parts by mass, the unexposed part may be poorly developed or the storage stability of the composition may be lowered.
  • the component (E) is a cross-linking agent, which is introduced into the composition when the photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A). Specific examples will be given below, but the present invention is not limited to these.
  • the thermal cross-linking agent is selected from, for example, a cross-linking compound having two or more substituents selected from (E1) alkoxymethyl group and hydroxymethyl group, and (E2) cross-linking compound represented by the following formula (2). Is preferable. These cross-linking agents can be used alone or in combination of two or more.
  • the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group of the component (E1) is exposed to a high temperature during heat curing, the crosslinking reaction proceeds by the dehydration condensation reaction. ..
  • examples of such compounds include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.
  • alkoxymethylated glycol uryl examples include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrax (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone.
  • alkoxymethylated benzoguanamine examples include tetramethoxymethylbenzoguanamine.
  • Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
  • alkoxymethylated melamine examples include hexamethoxymethylmelamine and the like.
  • Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)).
  • it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • a melamine compound a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.
  • phenoplast compound examples include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, and 3 , 3', 5,5'-tetrax (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl) Ethiliden) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6- Bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol], 2,6-bis (methoxymethyl) cresol, 2 , 6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4
  • an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.
  • Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
  • Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
  • the weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.
  • the photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the following formula (2) as the component (E2).
  • k represents an integer of 2 to 10
  • m represents an integer of 0 to 4
  • R represents a k-valent organic group.
  • the component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
  • 252 Product name of Nagase ChemteX Corporation
  • CY175, CY177, CY179 Product name of Huntsman Corporation
  • Araldite CY-182, CY-192, CY-184 Product name of Huntsman Corporation
  • Epicron 200, 400 aboveve, DIC Co., Ltd. product name
  • Epicoat 871, 872 aboveve, Mitsubishi Chemical Co., Ltd. product name
  • ED-5661, ED-5662 aboveve, Ceranies Coating
  • Product name manufactured by Huntsman Corporation etc.
  • these crosslinkable compounds can be used alone or in combination of two or more.
  • the compounds represented by the formulas E2-1 and E2-2 which have a cyclohexene oxide structure from the viewpoint of process resistance such as heat resistance, solvent resistance, long-term firing resistance, and transparency, epolide.
  • GT-401, GT-403, GT-301, GT-302, sinterside 2021, and seroxside 3000 are preferable.
  • the E component is a structure bridged by a thermal reaction with a heat-reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A) other than those shown as the component (E1) and the component (E2).
  • a heat-reactive site for example, a carboxyl group and / or a phenolic hydroxy group
  • Compounds that can form the above can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane.
  • a polymer having two or more structures capable of forming a bridging structure by a thermal reaction with the heat-reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A) is used.
  • the heat-reactive site for example, a carboxyl group and / or a phenolic hydroxy group
  • the component (A) is used.
  • 3-methacryloxypropyltrimethoxy a polymer produced using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxide cyclohexylmethyl methacrylate, or 3,4-epoxide cyclohexylmethyl methacrylate.
  • component (E) When the component (A) has a group that reacts with at least one group selected from the group consisting of a group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group, the hydroxy group, the carboxyl group and the amide group , A compound having two or more groups represented by amino groups can be used as the component (E).
  • crosslinkable compounds can be used alone or in combination of two or more.
  • the content is 1 part by mass to 50 parts by mass, preferably 1 part by mass or more with respect to 100 parts by mass of the component (A). It is 40 parts by mass, more preferably 1 part to 30 parts by mass.
  • the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation is improved. May not be obtained.
  • it exceeds 50 parts by mass an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the photosensitive resin composition Storage stability may deteriorate.
  • the component (F) is a compound having two or more ethylenically polymerizable groups.
  • the term "compound having two or more ethylenically polymerizable groups" as used herein means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular ends. , Those polymerizable groups mean at least one kind of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
  • the compound having two or more ethylenically polymerizable groups as the component (F) has good compatibility with each component in the solution of the negative type photosensitive resin composition in the photosensitive resin composition of the present invention. Moreover, from the viewpoint of not affecting the developability, a compound having a molecular weight (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.
  • such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and penta.
  • polyfunctional acrylate compound can be easily obtained as a commercially available product, and specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, and D-330.
  • the content is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts to 150 parts by mass, and particularly preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, tack may occur in the coating film after prebaking, or the unexposed portion may be poorly dissolved during development.
  • the component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid.
  • the functional group that forms a covalent bond with such an acid include an epoxy group, an alkoxymethyl group, and a hydroxymethyl group.
  • Examples of the compound having two or more epoxy groups include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, and glycerol.
  • Triglycidyl ether diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, diglycidyl 1,2-cyclohexanedicarboxylate Esters, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethanetriglycidyl ether and bisphenol-A-diglycidyl ether, And pentaerythritol polyglycidyl ether and the like.
  • the compound having two or more epoxy groups a commercially available compound may be used because it is easily available. Specific examples (trade names) thereof are given below, but the present invention is not limited to these: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.); Epoxy GT- Epoxy resins having a cyclohexene oxide structure such as 401, GT-403, GT-301, GT-302, seroxide 2021, seroxide 3000 (manufactured by Daicel Co., Ltd.); Epicoat 1001, 1002, 1003, 1004 , 1007, 1009, 1010, 828 (above, oiled shell epoxy Co., Ltd.
  • epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.)
  • Epoxy GT- Epoxy resins having a cyclohexene oxide structure such as 401, GT
  • a polymer having an epoxy group can also be used as the compound having two or more epoxy groups.
  • the polymer having an epoxy group can be produced, for example, by addition polymerization using an addition-polymerizable monomer having an epoxy group.
  • addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and polycondensation polymers such as epoxy novolac. ..
  • the polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin and glycidyltosilicate.
  • the weight average molecular weight of such a polymer is, for example, 300 to 20,000.
  • Examples of the compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds. ..
  • alkoxymethylated glycol uryl are as described in the above paragraph [0100].
  • alkoxymethylated benzoguanamine are as described in the above paragraph [0101].
  • alkoxymethylated melamine are as described in the above paragraph [0102].
  • it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • a melamine compound a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group.
  • Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.
  • an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.
  • Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl.
  • Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate.
  • the weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.
  • the photosensitive resin composition of the present invention contains a compound having two or more functional groups forming a covalent bond with the acid of the component (G), the content is 5% by mass based on 100 parts by mass of the component (A). It is preferably parts to 200 parts by mass, and more preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease, while if it is excessive, the developability of the unexposed portion deteriorates and the residual film or residue may be deteriorated. It may be the cause.
  • the component (H) is an adhesion promoter.
  • the photosensitive resin composition of the present invention may be added with an adhesion accelerator for the purpose of improving the adhesion to the substrate after development.
  • adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane.
  • the above-mentioned adhesion promoter is, for example, manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials World Inc. Commercially available compounds such as those manufactured by Toray Dow Corning Silicone Co., Ltd. and those manufactured by Toray Dow Corning Silicone Co., Ltd. can also be used, and these commercially available products are easily available.
  • alkoxysilanes that is, silane coupling agents
  • Silane coupling agents are preferable in that good adhesion can be obtained.
  • the amount of these adhesion promoters added is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). If 20 parts by mass or more is used, the sensitivity may decrease, and if it is less than 0.1 parts by mass, a sufficient effect of the adhesion accelerator may not be obtained.
  • the photosensitive resin composition used in the present invention is, if necessary, a leveling agent, a rheology adjuster, a pigment, a dye, a storage stabilizer, a defoaming agent, and a surfactant, as long as the effects of the present invention are not impaired.
  • a dissolution accelerator such as a polyhydric phenol or a polyvalent carboxylic acid can be contained.
  • the photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (A), (B), (C) and (D), and if desired, (E).
  • a cross-linking agent for the component a compound having two or more ethylenically polymerizable groups for the component (F), a compound having two or more functional groups forming a covalent bond with the acid of the component (G), and promoting adhesion of the component (H). It is a composition capable of further containing one or more of the agent and other additives.
  • C) component Solvent
  • D Photosensitizer
  • Preferred examples of the photosensitive resin composition used in the present invention are as follows. [1]: A photosensitive resin composition containing 0.01 part by mass to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and these components are dissolved in the component (C). [2]: The component (B) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass. A photosensitive resin composition in which the component (D) is a component (D-1).
  • the component (B) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass.
  • the photosensitive resin composition dissolved in the component, and the cross-linking agent which is the component (E) is further added by mass 1 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B).
  • a photosensitive resin composition partially contained, wherein the component (D) is a component (D-1).
  • the proportion of the solid content in the photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass. For example, it is 5% by mass to 60% by mass, or 10% by mass to 50% by mass.
  • the solid content refers to a product obtained by removing the component (C) from all the components of the photosensitive resin composition.
  • the method for preparing the photosensitive resin composition used in the present invention is not particularly limited, but as the method for preparing the photosensitive resin composition, for example, the component (B) is dissolved in the component (C) and the component (A) is alkali-soluble in this solution.
  • a covalent bond is formed by a resin, a photosensitizer of component (D), a cross-linking agent of component (E) if necessary, a compound having two or more ethylenically polymerizable groups of component (F), and an acid of component (G).
  • the solution of the copolymer obtained by the polymerization reaction in the component (C) can be used as it is, and in this case, it is exposed to the solution of the component (B).
  • the component (A), the component (D), and if necessary, the component (E), the component (F), the component (G), the component (H), etc. are added to form a uniform solution.
  • the component (C) may be additionally added for the purpose of adjusting the concentration.
  • the component (C) used in the process of forming the specific copolymer and the component (C) used for adjusting the concentration at the time of preparing the photosensitive resin composition may be the same or different. May be good.
  • the prepared solution of the photosensitive resin composition is used after being filtered using a filter having a pore size of about 0.2 ⁇ m or the like.
  • the photosensitive resin composition of the present invention comprises a substrate coated with a suitable substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium, etc., glass substrate). , Quartz substrate, ITO (Indium Tin Oxide, hereinafter referred to as ITO) substrate, etc.) and film (for example, triacetyl cellulose film, cycloolefin polymer film, cycloolefin copolymer film, polyethylene terephthalate film, polyester film, acrylic film, polyimide, etc.
  • a suitable substrate for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium, etc., glass substrate.
  • quartz substrate for example, Quartz substrate, ITO (Indium Tin Oxide, hereinafter referred to as ITO) substrate, etc.
  • film for example, triacetyl cellulose film, cycloolefin polymer
  • Resin film is applied by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet method, etc., and then pre-dried with a hot plate or oven. By doing so, a coating film can be formed. Then, by heat-treating this coating film, a photosensitive resin film as an underlayer film, a resist film, or the like is formed.
  • a heating temperature and a heating time appropriately selected from a temperature range of 70 ° C. to 160 ° C. and a time range of 0.3 to 60 minutes are adopted.
  • the heating temperature and heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes.
  • the film thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 ⁇ m to 30 ⁇ m, for example, 0.2 ⁇ m to 10 ⁇ m, and further, for example, 0.3 ⁇ m to 8 ⁇ m.
  • a sharp relief pattern on the end face can be obtained by heating the washed-out and remaining patterned film at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as needed.
  • alkaline developing solution examples include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
  • alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide
  • hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline.
  • examples thereof include an aqueous solution of quaternary ammonium and an alkaline aqueous solution such as an aqueous solution of amines such as ethanolamine, propylamine and ethylenediamine.
  • a surfactant or the like can be added to these developers.
  • a 0.1 to 2.58 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developing solution for a photoresist, and the photosensitive resin composition of the present invention also uses this alkaline developing solution. , It is possible to develop well without causing problems such as swelling of the film.
  • any of the liquid filling method, the dipping method, the rocking dipping method and the like can be used.
  • the developing time at that time is usually 15 to 180 seconds.
  • the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and form a pattern.
  • the finished film is obtained.
  • the pattern-forming film is post-baked for thermosetting, and specifically, by heating it using a hot plate, an oven, or the like, heat resistance, transparency, flattening property, etc.
  • a film having a good relief pattern with excellent low water absorption and chemical resistance can be obtained.
  • Post-baking is generally performed at a heating temperature selected from the temperature range of 140 ° C. to 270 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. The method is adopted.
  • the desired cured film having a good pattern shape can be obtained.
  • the double bank of the present invention refers to a first bank and a second bank.
  • the double bank forming process if the second bank exerts a separating function, the wettability of the upper layer material laminated by the first bank is improved, and coating unevenness can be suppressed, the first bank and the second bank
  • the arrangement pattern of banks is not particularly limited.
  • the contact angle of each bank is not limited as long as the wettability of the first bank is improved and the partitioning function of the second bank is exhibited. That is, the contact angle of the first bank may be larger, smaller, or the same as the contact angle of the second bank. From the viewpoint of suppressing coating unevenness of the upper layer materials to be laminated, it is preferable that the contact angle of the first bank is smaller than the contact angle of the second bank.
  • FIG. 4A is a schematic cross-sectional view of the BB'cut surface in FIG. 3, and the second banks 23 and 24 are shown in the first banks 13 and 14 shown in FIG. 4A. It is formed at an adjacent position.
  • the first bank has a structure intersecting with the second bank, and the second bank has a structure arranged directly above the first bank or via another layer. For example, as shown in FIGS. 1 and 2, the first bank 11 and the second banks 21 and 22 are formed so as to intersect with each other.
  • FIG. 1 and 2 the first bank 11 and the second banks 21 and 22 are formed so as to intersect with each other.
  • FIG. 2 is a cross-sectional view of the AA'cut surface of the structure 100 in FIG. 1, and as shown in FIG. 2, the second banks 21 and 22 are formed on the first bank 11. That is, the second banks 21 and 22 are formed after the first bank 11 is formed.
  • FIG. 4B is a schematic cross-sectional view of the CC'cut surface in FIG. 3, and as shown in FIG. 4B, the second bank 23 is above the first bank 12. , 24 are formed.
  • FIG. 5 is a plan view showing an arrangement pattern of the first bank and the second bank as an example.
  • the height of the first bank from the substrate surface remains lower than the height of the second bank from the substrate surface.
  • the cured film (bank) formed by the photosensitive resin composition of the present invention is drawn directly on the substrate, but this is just an example.
  • Other layers that can be formed on the substrate include, for example, an organic electroluminescence element, a QD-OLED display, a micro LED display, and the like.
  • an organic electroluminescence element an anode, a cathode, a hole injection layer, and a positive layer.
  • examples thereof include a hole transport layer, an electron injection layer, an electron transport layer, an electron block layer, and a light emitting layer.
  • the hole injection layer of the organic electroluminescence device is particularly suitable as another layer.
  • the other layer consists of at least one layer.
  • the number average molecular weight and weight average molecular weight of the specific copolymer and the specific crosslinked product obtained according to the following synthesis examples were determined by using a GPC apparatus manufactured by JASCO Corporation (Shodex® columns KF803L and KF804L) as an elution solvent. The measurement was carried out under the condition that tetrahydrofuran was allowed to flow through the column (column temperature 40 ° C.) at a flow rate of 1 ml / min to elute.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • the obtained acrylic polymer had Mn of 4,100 and Mw of 7,600.
  • Acrylic polymer solution (solid content concentration 30 mass) was obtained by dissolving 5.0 g of PFHMA, 3.8 g of KBM-503, 1.5 g of HEMA, and 0.5 g of AIBN in 25.32 g of PGME and reacting at 80 ° C. for 20 hours. %) was obtained (P2).
  • the obtained acrylic polymer had Mn of 4800 and Mw of 6700.
  • Example 1 ⁇ Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Upper Membrane Material>
  • the component (B), the component (C), the component (D) and the component (E) are mixed in a predetermined ratio with the solution of the component (A).
  • the solution of the component (A), the component (C), the component (D) and the component (E), and if necessary, the component (H), the surfactant and the liquid repellent component. was mixed at a predetermined ratio and stirred at room temperature for 3 hours to prepare a uniform solution to prepare a positive photosensitive resin composition for each Example, each Comparative Example and the upper film material.
  • a positive photosensitive resin composition was prepared with the composition shown in Table 1.
  • the composition ratio in Table 1 represents the ratio in terms of solid content.
  • TMAH tetramethylammonium hydroxide
  • a field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation was used to determine the pattern shape at the intersection of the 50 ⁇ m line pattern extending in the column direction and the 100 ⁇ m line pattern extending in the row direction. evaluated.
  • the examples have good coatability, and the contact angle is 5 degrees or less immediately after the cured film is formed, regardless of the presence or absence of the developing step or the surface modification step, and the excellent liquidity property is maintained.
  • the coatability was good, but the lipophilicity decreased immediately after the cured film was formed, and the surface of the photosensitive resin film was washed away during development to improve the lipophilicity, but the surface modification step was performed. And the positivity decreased.

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Abstract

[Problem] To provide a cured film with high liquid philicity formed from a photosensitive resin composition according to the present invention, the cured film being used in liquid-crystal display elements, organic EL display elements, etc. and inhibiting an overlying material from being unevenly applied thereon when disposed by an ink-jet method, a slit coating method, etc. [Solution] A photosensitive resin composition which is applied as a material for first banks in producing a display element including fixed individual pixel regions formed by disposing the first banks and second banks on a substrate directly or on another layer interposed therebetween, the photosensitive resin composition comprising the following ingredients (A), (B), (C), and (D). Ingredient (A): An alkali-soluble resin Ingredient (B): A thermally decomposable fluoropolymer Ingredient (C): A solvent Ingredient (D): A photosensitizer

Description

感光性樹脂組成物Photosensitive resin composition
　本発明は、感光性樹脂組成物及びそれから得られる硬化膜に関する。より詳細には、高い撥液性を硬化膜表面に有する画像を形成可能な感光性樹脂組成物及びその硬化膜、並びに該硬化膜を用いた各種材料に関する。この感光性樹脂組成物は、特に液晶ディスプレイやＥＬディスプレイにおける層間絶縁膜、インクジェット方式に対応した遮光材料や隔壁材料として用いるのに好適である。 The present invention relates to a photosensitive resin composition and a cured film obtained from the photosensitive resin composition. More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high liquid repellency on the surface of a cured film, a cured film thereof, and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in a liquid crystal display or an EL display, a light-shielding material compatible with an inkjet method, or a partition material.
　薄膜トランジスタ（ＴＦＴ）型液晶表示素子、有機エレクトロルミネッセンス素子等のディスプレイ素子の作製工程においてインクジェットを用いたフルカラー表示基板作製技術も近年活発に検討されている。たとえば液晶表示素子におけるカラーフィルタ作製に関しては、従来の印刷法、電着法、染色法または顔料分散法に対して、あらかじめパターニングされた画素を規定する区画（以下バンクという）を、光を遮断する感光性樹脂層で形成し、このバンクに囲まれた領域にインク滴を滴下するカラーフィルタおよびその製造方法（特許文献１）などが提案されている。
　しかしインクジェット法を使用した際、吐出の安定性に欠けるため膜厚ムラが発生するなど課題があった。そこで特許文献２では、並列方向に配置された複数の隔壁とインク流れ防止用板用部材を使用して画素を区画することにより、膜厚ムラを防止することが提案されている（特許文献２）。また格子状に交差する２種類のバンクを採用することにより、インク塗布時の混色の発生が抑制され、色純度の高い表示が可能になること（特許文献３）が提案されている。
　しかし、これら隔壁や板用部材上にインクを塗布する際、インクが隔壁および板用部材上や画素電極上に凝集してしまうことがあった。 In recent years, a full-color display substrate manufacturing technique using an inkjet has been actively studied in the manufacturing process of display elements such as thin film transistor (TFT) type liquid crystal display elements and organic electroluminescence elements. For example, regarding the production of color filters in liquid crystal display elements, light is blocked in a section (hereinafter referred to as a bank) that defines pre-patterned pixels in contrast to the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method. A color filter formed of a photosensitive resin layer and dropping ink droplets on a region surrounded by the bank and a method for producing the same have been proposed (Patent Document 1).
However, when the inkjet method is used, there are problems such as uneven film thickness due to lack of stability of ejection. Therefore, Patent Document 2 proposes to prevent uneven film thickness by partitioning pixels by using a plurality of partition walls and ink flow prevention plate members arranged in parallel (Patent Document 2). ). Further, it has been proposed that by adopting two types of banks that intersect in a grid pattern, the occurrence of color mixing during ink application is suppressed, and display with high color purity becomes possible (Patent Document 3).
However, when the ink is applied onto the partition wall or the plate member, the ink may aggregate on the partition wall or the plate member or the pixel electrode.
特開２０００－１８７１１１号公報Japanese Unexamined Patent Publication No. 2000-187111 特開２０１１－２３３０５号公報Japanese Unexamined Patent Publication No. 2011-23305 特願２０１８－５２７２５８Japanese Patent Application No. 2018-527258
　本発明は、上記の事情に鑑みなされたものであって、その解決しようとする課題は、液晶表示素子、有機エレクトロルミネッセンス素子等に使用され、本発明の感光性樹脂組成物により、高い親液性を有する硬化膜、またインクジェット法やスリットコート法等を使用し積層される上層材料の塗布ムラを抑制した硬化膜を提供することにある。 The present invention has been made in view of the above circumstances, and the problem to be solved is that it is used for a liquid crystal display element, an organic electroluminescence element, etc., and the photosensitive resin composition of the present invention provides a high base solution. An object of the present invention is to provide a cured film having a property, and a cured film that suppresses coating unevenness of the upper layer material laminated by using an inkjet method, a slit coating method, or the like.
　本発明は以下に関する。
１．第一バンクと第二バンクとを基板上に直接もしくは他の層を介して配設することにより、個々の画素域が画定されている表示素子において第一バンクの材料として適用される組成物であって、
　下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分を含有する感光性樹脂組成物。
（Ａ）成分：アルカリ可溶性樹脂
（Ｂ）成分：フッ素含有熱分解性重合体
（Ｃ）成分：溶剤
（Ｄ）成分：感光剤
２．基板上において、前記第一バンクは、前記第二バンクに隣接する位置に配置された構造、及び／又は前記第二バンクに囲まれた区域内に孤立して存在する構造、及び／又は前記第二バンクと交差する構造を成し、
　そして、前記第一バンクの基板面からの高さは、前記第二バンクの基板面からの高さよりもより低い上記１項に記載の感光性樹脂組成物。
３．基板上において、前記第二バンクは、前記第一バンクの上方に直接もしくは他の層を介して配置された構造を成し、
　そして、前記第一バンクの基板面からの高さは、前記第二バンクの基板面からの高さよりもより低い上記１項に記載の感光性樹脂組成物。
４．前記（Ｂ）成分であるフッ素含有熱分解性重合体は、重合性単量体の重合体構造を有する主鎖（ａ）と、下記一般式（１）で表される官能基を有する側鎖（ｂ）を有するフッ素含有熱分解性重合体である上記１項乃至上記３項のいずれか一項に記載の感光性樹脂組成物。
Figure JPOXMLDOC01-appb-C000003
 （式中、Ｒ１、Ｒ２及びＲ３はそれぞれ独立して水素原子または炭素原子数１～１８の有機基であり、Ｒ４はフッ素化アルキル基又はポリ（パーフルオロアルキレンエーテル）鎖である。Ｙ１は酸素原子または硫黄原子である。）
５．前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が１～６のフッ素化アルキル基である上記１項乃至上記４項のいずれか一項に記載の感光性樹脂組成物。
６．前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が４～６のフッ素化アルキル基である上記１項乃至上記４項のいずれか一項に記載の感光性樹脂組成物。
７．前記Ｒ１、Ｒ２およびＲ３がそれぞれ独立して水素原子であり、前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が１～６のフッ素化アルキル基である上記１項乃至上記４項のいずれか一項に記載の感光性樹脂組成物。
８．前記一般式（１）で表される側鎖（ｂ）が、下記式（１－１）で表されるものである上記１項乃至上記４項のいずれか一項に記載の感光性樹脂組成物。
Figure JPOXMLDOC01-appb-C000004
 ９．前記感光性樹脂組成物は、下記（Ｚ１）乃至（Ｚ４）のうち少なくともいずれか１つを満足する上記１項乃至上記８項のいずれか一項に記載の感光性樹脂組成物。
（Ｚ１）：（Ｅ）成分である架橋剤をさらに含有する
（Ｚ２）：前記アルカリ可溶性樹脂が、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基をさらに有する
（Ｚ３）：前記感光剤が光ラジカル発生剤であり、さらに、（Ｆ）成分としてエチレン性二重結合を２個以上有する化合物を含有する
（Ｚ４）：前記感光剤が光酸発生剤であり、さらに、（Ｇ）成分として前記光酸発生剤より発生した酸により共有結合を形成する官能基を２個以上有する化合物を含有する
１０．前記感光剤がキノンジアジド化合物である上記１項乃至上記９項のいずれか一項に記載の感光性樹脂組成物。
１１．前記感光剤がキノンジアジド化合物であり、さらに、前記（Ｚ１）又は（Ｚ２）のいずれかを満足する上記９項に記載の感光性樹脂組成物。
１２．前記感光剤がジアゾナフトキノンである上記１１項に記載の感光性樹脂組成物。
１３．前記アルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至５０，０００である上記１項乃至上記１２項のいずれか一項に記載の感光性樹脂組成物。
１４．前記アルカリ可溶性樹脂１００質量部に対して０．０１質量部乃至１質量部の前記フッ素含有熱分解性重合体を含有する上記１項乃至上記１３項のいずれか一項に記載の感光性樹脂組成物。
１５．前記アルカリ可溶性樹脂１００質量部に対して、前記架橋剤が１質量部乃至５０質量部である上記９項乃至上記１４項のいずれか一項に記載の感光性樹脂組成物。
１６．前記第二バンクと前記第一バンクで画定された画素域に有機薄膜を備える表示素子において、前記有機薄膜が有機エレクトロルミネッセンス素子の画素に用いる上記１項乃至上記１５項のいずれか一項に記載の感光性樹脂組成物。
１７．前記他の層が有機エレクトロルミネッセンス素子の正孔注入層である上記１項乃至上記１６項のいずれか一項に記載の感光性樹脂組成物。
１８．上記１項乃至上記１７項のいずれか一項に記載の感光性樹脂組成物により形成された硬化膜。
１９．上記１８項に記載の硬化膜を有する表示素子。
２０．第一バンクを基板上に直接もしくは他の層を介して形成する工程と、
第二バンクを基板上に直接もしくは他の層を介して形成する工程とを含み、
前記第一バンクは、上記１項乃至上記１７項のいずれ一項に記載の感光性樹脂組成物からなる、個々の画素域が画定されている表示素子の製造方法。 The present invention relates to the following.
1. 1. A composition that is applied as a material for the first bank in a display device in which individual pixel areas are defined by arranging the first bank and the second bank directly on the substrate or via another layer. There,
A photosensitive resin composition containing the following components (A), (B), (C) and (D).
(A) component: alkali-soluble resin (B) component: fluorine-containing pyrolytic polymer (C) component: solvent (D) component: photosensitizer 2. On the substrate, the first bank has a structure arranged adjacent to the second bank and / or a structure isolated in an area surrounded by the second bank, and / or the first bank. It has a structure that intersects with two banks,
The photosensitive resin composition according to item 1, wherein the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface.
3. 3. On the substrate, the second bank forms a structure arranged directly above the first bank or via another layer.
The photosensitive resin composition according to item 1, wherein the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface.
4. The fluorine-containing pyrolytic polymer, which is the component (B), has a main chain (a) having a polymer structure of a polymerizable monomer and a side chain having a functional group represented by the following general formula (1). The photosensitive resin composition according to any one of the above items 1 to 3 which is a fluorine-containing pyrolytic polymer having (b).
Figure JPOXMLDOC01-appb-C000003
 (In the formula, R 1 , R 2 and R 3 are independently hydrogen atoms or organic groups having 1 to 18 carbon atoms, and R 4 is a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain. . Y 1 is an oxygen atom or a sulfur atom.)
5. The photosensitive resin composition according to any one of the above items 1 to 4 , wherein R4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded.
6. The photosensitive resin composition according to any one of the above items 1 to 4 , wherein R4 is a fluorinated alkyl group having 4 to 6 carbon atoms to which a fluorine atom is directly bonded.
7. Items 1 to 2 above, wherein R 1 , R 2 and R 3 are independent hydrogen atoms, and R 4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded. The photosensitive resin composition according to any one of items 4.
8. The photosensitive resin composition according to any one of the above items 1 to 4, wherein the side chain (b) represented by the general formula (1) is represented by the following formula (1-1). Stuff.
Figure JPOXMLDOC01-appb-C000004
 9. The photosensitive resin composition according to any one of the above items 1 to 8, which satisfies at least one of the following (Z1) to (Z4).
(Z1): Further containing a cross-linking agent as a component (E) (Z2): The alkali-soluble resin further has a self-crosslinking group or is a group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Further having a group that reacts with at least one group selected from (Z3): The photosensitive agent is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as the component (F). (Z4): The photosensitizer is a photoacid generator, and further contains, as a component (G), a compound having two or more functional groups forming a covalent bond with the acid generated by the photoacid generator. The photosensitive resin composition according to any one of the above items 1 to 9, wherein the photosensitizer is a quinonediazide compound.
11. The photosensitive resin composition according to the above item 9, wherein the photosensitive agent is a quinonediazide compound, and further satisfies either (Z1) or (Z2).
12. The photosensitive resin composition according to the above item 11, wherein the photosensitive agent is diazonaphthoquinone.
13. The photosensitive resin composition according to any one of the above items 1 to 12, wherein the alkali-soluble resin has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
14. The photosensitive resin composition according to any one of the above items 1 to 13, which contains 0.01 part by mass to 1 part by mass of the fluorine-containing pyrolytic polymer with respect to 100 parts by mass of the alkali-soluble resin. Stuff.
15. The photosensitive resin composition according to any one of the above 9 to 14 parts, wherein the cross-linking agent is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
16. The item according to any one of the above items 1 to 15 in which the organic thin film is used for the pixels of the organic electroluminescence element in the display element provided with the organic thin film in the pixel area defined by the second bank and the first bank. Photosensitive resin composition.
17. The photosensitive resin composition according to any one of the above items 1 to 16, wherein the other layer is a hole injection layer of an organic electroluminescence device.
18. A cured film formed by the photosensitive resin composition according to any one of the above items 1 to 17.
19. The display element having the cured film according to the above item 18.
20. The process of forming the first bank directly on the substrate or via other layers,
Including the step of forming the second bank directly on the substrate or via other layers.
The first bank is a method for manufacturing a display element in which individual pixel regions are defined, which comprises the photosensitive resin composition according to any one of the above items 1 to 17.
　本発明の感光性樹脂組成物は、高い親液性を示す。本発明の感光性樹脂組成物により形成される硬化膜は、高い親液性を示しながら、インクジェット法やスリットコート法等を使用し積層される上層材料の濡れ性が向上され、塗布ムラを抑制することができる。そして、本発明の硬化膜を有する表示素子は、インク塗布時にインクが隔壁および板用部材上や画素電極上に凝集しなくなることにより、混色の発生が抑制され、色純度の高い表示が可能である。 The photosensitive resin composition of the present invention exhibits high liquidity. The cured film formed by the photosensitive resin composition of the present invention has high wettability of the upper layer material laminated by using an inkjet method, a slit coating method, or the like while exhibiting high liquid-forming property, and suppresses coating unevenness. can do. In the display element having the cured film of the present invention, the ink does not aggregate on the partition wall and the plate member or the pixel electrode when the ink is applied, so that the occurrence of color mixing is suppressed and the display with high color purity is possible. is there.
図１は、第一バンク及び第二バンクが形成された構造１００の斜視図である。FIG. 1 is a perspective view of the structure 100 in which the first bank and the second bank are formed. 図２は、図１における構造１００のＡ－Ａ’切断面の断面図である。FIG. 2 is a cross-sectional view of the AA'cut surface of the structure 100 in FIG. 図３は、第一バンク及び第二バンクが形成された構造２００の斜視図である。FIG. 3 is a perspective view of the structure 200 in which the first bank and the second bank are formed. 図４は、図３における構造２００の断面図であり、（ａ）は図３におけるＢ－Ｂ’切断面の断面図であり、（ｂ）は、図３におけるＣ－Ｃ’切断面の模式的な断面図である。4A and 4B are cross-sectional views of the structure 200 in FIG. 3, FIG. 4A is a cross-sectional view of a BB'cut surface in FIG. 3, and FIG. 4B is a schematic diagram of a CC'cut surface in FIG. Cross-sectional view. 図５は、変形例として第一バンク及び第二バンクの配置を表す平面図であり、（ａ）は第一バンクの基板面からの高さの変化を表す変形例を示し、（ｂ）は（ａ）に基づき、第一バンクの基板面からの高さの変化がさらに複雑になる変形例を示す。FIG. 5 is a plan view showing the arrangement of the first bank and the second bank as a modification, FIG. 5A shows a modification showing a change in height of the first bank from the substrate surface, and FIG. 5B shows a modification. Based on (a), a modified example in which the change in height from the substrate surface of the first bank becomes more complicated is shown.
　以下、本発明の感光性樹脂組成物、当該感光性樹脂組成物により形成される硬化膜及び当該硬化膜を有する表示素子の製造方法について、詳細に説明する。 Hereinafter, the method for producing the photosensitive resin composition of the present invention, the cured film formed by the photosensitive resin composition, and the display element having the cured film will be described in detail.
＜感光性樹脂組成物＞
　以下、感光性樹脂組成物の各成分の詳細を説明する。 <Photosensitive resin composition>
The details of each component of the photosensitive resin composition will be described below.
＜（Ａ）成分＞
　本発明の（Ａ）成分は、アルカリ可溶性樹脂である。該樹脂にはアルカリ可溶性を付与すべくアルカリ可溶性基が含まれアルカリ可溶性基としては、例えば、フェノール性ヒドロキシ基、カルボキシル基、酸無水物基、イミド基、スルホニル基、リン酸、ボロン酸及び活性メチレン基および活性メチン基が挙げられる。 <Ingredient (A)>
The component (A) of the present invention is an alkali-soluble resin. The resin contains an alkali-soluble group to impart alkali solubility, and examples of the alkali-soluble group include phenolic hydroxy group, carboxyl group, acid anhydride group, imide group, sulfonyl group, phosphoric acid, boric acid and activity. Examples include a methylene group and an active methine group.
　活性メチレン基とはメチレン基（－ＣＨ２－）のうち、隣接位置にカルボニル基を持ち、求核試薬に対する反応性を持つものを言う。また、本発明において前記活性メチン基とは前記活性メチレン基においてメチレン基の１個の水素原子がアルキル基で置換された構造を有し、求核試薬に対する反応性を持つものを言う。 The active methylene group refers to a methylene group (-CH 2- ) having a carbonyl group at an adjacent position and having reactivity with a nucleophile. Further, in the present invention, the active methine group refers to an active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group and having reactivity with a nucleophile.
　活性メチレン基および活性メチン基の中でも活性メチレン基が好ましく下記式（ａ１）で表される活性メチレン基がより好ましい。
Figure JPOXMLDOC01-appb-C000005
 （式（ａ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） Among the active methylene group and the active methine group, the active methylene group is preferable, and the active methylene group represented by the following formula (a1) is more preferable.
Figure JPOXMLDOC01-appb-C000005
 (In the formula (a1), R represents an alkyl group, an alkoxy group or a phenyl group, and the broken line represents a bond.)
　上記式（ａ１）において、Ｒが表すアルキル基としては、例えば、炭素原子数１乃至２０のアルキル基が挙げられ、炭素原子数１乃至５のアルキル基が好ましい。
　そのようなアルキル基としては、例えば、メチル基、エチル基、ｎ－プロピル基、ｉ－プロピル基等が挙げられる。
　その中でも、メチル基、エチル基、ｎ－プロピル基等が好ましい。 In the above formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, and alkyl groups having 1 to 5 carbon atoms are preferable.
Examples of such an alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group and the like.
Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.
　上記式（ａ１）において、Ｒが表すアルコキシ基としては、例えば、炭素原子数１乃至２０のアルコキシ基が挙げられ、炭素原子数１乃至５のアルコキシ基が好ましい。
　そのようなアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉ－プロポキシ基、ｎ－ブトキシ基、ｉ－ブトキシ基、ｓ－ブトキシ基、ｔ－ブトキシ基等が挙げられる。
　その中でも、メトキシ基、エトキシ基及びｎ－プロポキシ基等が好ましい。 In the above formula (a1), examples of the alkoxy group represented by R include an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such an alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group and the like.
Among them, a methoxy group, an ethoxy group, an n-propoxy group and the like are preferable.
　上記式（ａ１）で表される基としては、例えば、以下の構造等が挙げられる。なお、構造式中、破線は結合手を表す。
Figure JPOXMLDOC01-appb-C000006
 Examples of the group represented by the above formula (a1) include the following structures and the like. In the structural formula, the broken line represents the bond.
Figure JPOXMLDOC01-appb-C000006
　上記アルカリ可溶性基の中でも、フェノール性ヒドロキシ基及びカルボキシル基からなる群から選択される少なくとも１種の有機基を有し、且つ、数平均分子量が２，０００乃至５０，０００であるアルカリ可溶性樹脂であることが好ましい。 Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable to have.
　上記（Ａ）成分のアルカリ可溶性樹脂は、かかる構造を有するアルカリ可溶性樹脂であればよく、樹脂を構成する高分子の主鎖の骨格及び側鎖の種類などについて特に限定されない。 The alkali-soluble resin of the component (A) may be any alkali-soluble resin having such a structure, and the type of the main chain skeleton and side chains of the polymer constituting the resin is not particularly limited.
　然しながら、（Ａ）成分のアルカリ可溶性樹脂は、数平均分子量が２，０００乃至５０，０００の範囲内にあるものである。数平均分子量が５０，０００を超えて過大なものであると、現像残渣が発生し易くなり、感度が大きく低下する一方、数平均分子量が２，０００未満で過小なものであると、現像の際、露光部の膜減りが相当量発生し、硬化不足になる場合がある。 However, the alkali-soluble resin of the component (A) has a number average molecular weight in the range of 2,000 to 50,000. If the number average molecular weight is more than 50,000 and is excessive, development residue is likely to be generated and the sensitivity is greatly lowered, while if the number average molecular weight is less than 2,000 and is too small, the development is carried out. At that time, a considerable amount of film loss may occur in the exposed area, resulting in insufficient curing.
　（Ａ）成分のアルカリ可溶性樹脂としては、例えばアクリル系樹脂、ポリヒドロキシスチレン系樹脂、あるいはポリイミド前駆体又はポリイミド等が挙げることができる。 Examples of the alkali-soluble resin of the component (A) include an acrylic resin, a polyhydroxystyrene resin, a polyimide precursor, and a polyimide.
　また、本発明においては、複数種のモノマーを重合して得られる共重合体（以下、特定共重合体と称す。）からなるアルカリ可溶性樹脂を（Ａ）成分として用いることもできる。この場合、（Ａ）成分のアルカリ可溶性樹脂は、複数種の特定共重合体のブレンド物であってもよい。 Further, in the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing a plurality of types of monomers (hereinafter referred to as a specific copolymer) can also be used as the component (A). In this case, the alkali-soluble resin of the component (A) may be a blend of a plurality of specific copolymers.
　すなわち、上記の特定共重合体は、アルカリ可溶性を発現するモノマー、即ちフェノール性ヒドロキシ基及びカルボキシル基からなる群から選択される少なくとも一種を有するモノマーと、これらモノマーと共重合可能なモノマーの群から選択される少なくとも一種のモノマーとを、必須の構成単位として形成された共重合体であって、その数平均分子量が２，０００乃至５０，０００のものである。数平均分子量が５０，０００より過大であると、残渣が生じる場合がある。 That is, the above-mentioned specific copolymer consists of a monomer that expresses alkali solubility, that is, a monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group, and a group of monomers copolymerizable with these monomers. It is a copolymer formed by using at least one selected monomer as an essential constituent unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.
　上記の「フェノール性ヒドロキシ基及びカルボキシル基からなる群から選択される少なくとも一種を有するモノマー」は、フェノール性ヒドロキシ基を有するモノマー及びカルボキシル基を有するモノマーが含まれる。これらのモノマーはフェノール性ヒドロキシ基又はカルボキシル基を一個有するものに限らず、複数個有するものでもよい。 The above-mentioned "monomer having at least one selected from the group consisting of a phenolic hydroxy group and a carboxyl group" includes a monomer having a phenolic hydroxy group and a monomer having a carboxyl group. These monomers are not limited to those having one phenolic hydroxy group or carboxyl group, and may have a plurality of these monomers.
　以下、上記モノマーの具体例を挙げるが、これらに限定されるものでない。
　カルボキシル基を有するモノマーとしては、例えば、アクリル酸、メタクリル酸、クロトン酸、モノ－（２－（アクリロイルオキシ）エチル）フタレート、モノ－（２－（メタクリロイルオキシ）エチル）フタレート、Ｎ－（カルボキシフェニル）マレイミド、Ｎ－（カルボキシフェニル）メタクリルアミド、Ｎ－（カルボキシフェニル）アクリルアミド等が挙げられる。 Specific examples of the above-mentioned monomers will be given below, but the present invention is not limited thereto.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- (2- (methacryloyloxy) ethyl) phthalate, and N- (carboxyphenyl). ) Maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide and the like.
　フェノール性ヒドロキシ基を有するモノマーとしては、例えば、ヒドロキシスチレン、Ｎ－（ヒドロキシフェニル）アクリルアミド、Ｎ－（ヒドロキシフェニル）メタクリルアミド、Ｎ－（ヒドロキシフェニル）マレイミド、４－ヒドロキシフェニルメタクリレート等が挙げられる。 Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4-hydroxyphenyl methacrylate and the like.
　（Ａ）成分のアルカリ可溶性樹脂の製造における不飽和カルボン酸誘導体及び／またはフェノール性ヒドロキシ基と重合性不飽和基を有するモノマーの比率は、（Ａ）成分のアルカリ可溶性樹脂の製造に用いる全てのモノマーのうち、好ましくは５モル％乃至９０モル％、より好ましくは１０モル％乃至６０モル％、最も好ましくは１０モル％乃至３０モル％である。不飽和カルボン酸誘導体が５重量％未満の場合には、重合体のアルカリ溶解性が不足する。 The ratio of the unsaturated carboxylic acid derivative and / or the monomer having a phenolic hydroxy group and the polymerizable unsaturated group in the production of the alkali-soluble resin of the component (A) is all used in the production of the alkali-soluble resin of the component (A). Of the monomers, it is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, and most preferably 10 mol% to 30 mol%. When the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.
　本発明の（Ａ）成分であるアルカリ可溶性樹脂は、硬化後のパターン形状をより安定化させるという点から、さらにヒドロキシアルキル基と重合性不飽和基とを有するモノマーを共重合させたものであることが好ましい。 The alkali-soluble resin which is the component (A) of the present invention is obtained by further copolymerizing a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the pattern shape after curing. Is preferable.
　ヒドロキシアルキル基と重合性不飽和基とを有するモノマーとしては、例えば、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレート、４－ヒドロキシブチルアクリレート、２，３－ジヒドロキシプロピルアクリレート、２－ヒドロキシエチルメタクリレート、２－ヒドロキシプロピルメタクリレート、４－ヒドロキシブチルメタクリレート、２，３－ジヒドロキシプロピルメタクリレート、グリセリンモノメタクリレート、５－アクリロイルオキシ－６－ヒドロキシノルボルネン－２－カルボキシリック－６－ラクトン等が挙げられる。 Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, and 2-hydroxyethyl methacrylate. Examples thereof include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone and the like.
　（Ａ）成分のアルカリ可溶性樹脂の製造におけるヒドロキシアルキル基と重合性不飽和基とを有するモノマーの比率は、好ましくは５質量％乃至６０質量％、より好ましくは１０質量％乃至５０質量％、最も好ましいのは２０質量％乃至４０質量％である。ヒドロキシアルキル基と重合性不飽和基とを有するモノマーが５質量％未満の場合は共重合体のパターン形状の安定化効果が得られない場合がある。６０質量％以上の場合には、（Ａ）成分のアルカリ可溶性基が不足し、現像性等の特性が低下する場合がある。 The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble resin of the component (A) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, most preferably. It is preferably 20% by mass to 40% by mass. If the amount of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 5% by mass, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If it is 60% by mass or more, the alkali-soluble group of the component (A) may be insufficient, and the properties such as developability may be deteriorated.
　本発明の（Ａ）成分であるアルカリ可溶性樹脂は、共重合体のガラス転移温度（以下Ｔｇと称す）を上げるという点から、さらにＮ置換マレイミド化合物を共重合させたものであることが好ましい。 The alkali-soluble resin as the component (A) of the present invention is preferably a copolymer of an N-substituted maleimide compound from the viewpoint of raising the glass transition temperature (hereinafter referred to as Tg) of the copolymer.
　Ｎ置換マレイミド化合物としては、例えば、Ｎ－メチルマレイミド、Ｎ－エチルマレイミド、Ｎ－フェニルマレイミド、及びＮ－シクロヘキシルマレイミド等が挙げられる。透明性の観点から芳香環を有さない物が好ましく、現像性、透明性、耐熱性の点から脂環骨格を有するものがより好ましく、中でもシクロヘキシルマレイミドが最も好ましい。 Examples of the N-substituted maleimide compound include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferable, those having an alicyclic skeleton are more preferable from the viewpoint of developability, transparency and heat resistance, and cyclohexylmaleimide is most preferable.
　（Ａ）成分のアルカリ可溶性樹脂の製造におけるＮ置換マレイミドの比率は、好ましくは５質量％乃至６０質量％、より好ましくは１０質量％乃至５０質量％、最も好ましいのは２０質量％乃至４０質量％である。Ｎ置換マレイミドが５質量％未満の場合は共重合体のＴｇが低くなり、耐熱性に劣る場合がある。６０質量％以上の場合には、透明性が低下する場合がある。 The ratio of the N-substituted maleimide in the production of the alkali-soluble resin of the component (A) is preferably 5% by mass to 60% by mass, more preferably 10% by mass to 50% by mass, and most preferably 20% by mass to 40% by mass. Is. When the N-substituted maleimide is less than 5% by mass, the Tg of the copolymer becomes low, and the heat resistance may be inferior. If it is 60% by mass or more, the transparency may decrease.
　本発明の感光性樹脂組成物が要件（Ｚ２）を満足する場合、本発明で用いられる（Ａ）成分のアルカリ可溶性樹脂は、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基（以下、架橋性基ともいう）をさらに有する共重合体であることが好ましい。 When the photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin of the component (A) used in the present invention further has a self-crosslinking group, or has a hydroxy group, a carboxyl group, or an amide. It is preferably a copolymer further having a group (hereinafter, also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of a group and an amino group.
　上記自己架橋性基としてはＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基が挙げられる。 Examples of the self-crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate group.
　上記架橋性基としては、Ｎ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等が挙げられる。 Examples of the crosslinkable group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a blocked isocyanate group and the like.
　かかる自己架橋性基又は架橋性基を（Ａ）成分のアルカリ可溶性樹脂に含有させる場合の含有量は、（Ａ）成分の樹脂における繰り返し単位１単位あたり、０．１乃至０．９個であることが好ましく、現像性と耐溶剤性の観点から、０．１乃至０．８個であることがさらに好ましい。 When the self-crosslinkable group or the crosslinkable group is contained in the alkali-soluble resin of the component (A), the content is 0.1 to 0.9 per repeating unit in the resin of the component (A). It is preferable, and from the viewpoint of developability and solvent resistance, 0.1 to 0.8 is more preferable.
　（Ａ）成分のアルカリ可溶性樹脂が、さらにＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の自己架橋性基及びＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の架橋性基から選ばれる少なくとも１種を有する繰り返し単位を有する場合、例えば、ラジカル重合性を有し、エポキシ基、オキセタン基、ビニル基、ブロックイソシアネート基等の架橋性基及びＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基及びアルコキシシリル基等の自己架橋性基から選ばれる少なくとも１種を有する不飽和化合物を共重合させればよい。 The alkali-soluble resin of the component (A) further includes self-crosslinking groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and blocked isocyanate group, and N-alkoxymethyl. When it has a repeating unit having at least one selected from a crosslinkable group such as a group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group, for example, it has radical polymerizable property and is epoxy. An unsaturated compound having at least one selected from a crosslinkable group such as a group, an oxetane group, a vinyl group and a blocked isocyanate group and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group and an alkoxysilyl group. It may be copolymerized.
　ラジカル重合性を有し、Ｎ－アルコキシメチル基を有する不飽和化合物としては、Ｎ－ブトキシメチルアクリルアミド、Ｎ－イソブトキシメチルアクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－メチロールアクリルアミド等が挙げられる。 Examples of unsaturated compounds having radical polymerizable properties and an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. And so on.
　ラジカル重合性を有し、さらにＮ－ヒドロキシメチル基を有するモノマーとしては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－ヒドロキシメチルメタクリルアミド等が挙げられる。 Examples of the monomer having radical polymerizable property and further having an N-hydroxymethyl group include N-hydroxymethylacrylamide and N-hydroxymethylmethacrylamide.
　ラジカル重合性を有し、さらにアルコキシシリル基を有するモノマーとしては、３－アクリロイルオキシトリメトキシシラン、３－アクリロイルオキシトリエトキシシラン、３－メタクリロイルオキシトリメトキシシラン、３－メタクリロイルオキシトリエトキシシラン等が挙げられる。 Examples of the monomer having radical polymerization property and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.
　ラジカル重合性を有し、さらにエポキシ基を有する不飽和化合物としては、例えばアクリル酸グリシジル、メタクリル酸グリシジル、α－エチルアクリル酸グリシジル、α－ｎ－プロピルアクリル酸グリシジル、α－ｎ－ブチルアクリル酸グリシジル、アクリル酸－３，４－エポキシブチル、メタクリル酸－３，４－エポキシブチル、アクリル酸－６，７－エポキシヘプチル、メタクリル酸－６，７－エポキシヘプチル、α－エチルアクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、３，４－エポキシシクロへキシルメタクリレートなどが挙げられる。これらのうち、メタクリル酸グリシジル、メタクリル酸－６，７－エポキシヘプチル、ｏ－ビニルベンジルグリシジルエーテル、ｍ－ビニルベンジルグリシジルエーテル、ｐ－ビニルベンジルグリシジルエーテル、３，４－エポキシシクロへキシルメタクリレートなどが好ましく用いられる。これらは、単独であるいは組み合わせて用いられる。 Examples of unsaturated compounds having radical polymerizable properties and having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, and α-n-butylacrylic acid. Glycidyl, acrylate-3,4-epoxybutyl, methacrylate-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylate-6,7-epoxyheptyl, α-ethylacrylic acid-6, Examples thereof include 7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate and the like It is preferably used. These may be used alone or in combination.
　ラジカル重合性を有し、さらにオキセタン基を有する不飽和化合物としては、例えば、オキセタン基を有する（メタ）アクリル酸エステルなどを挙げることができる。なお、このようなモノマーの中では、３－（メタクリロイルオキシメチル）オキセタン、３－（アクリロイルオキシメチル）オキセタン、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン、３－（メタクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（アクリロイルオキシメチル）－２－トリフロロメチルオキセタン、３－（メタクリロイルオキシメチル）－２－フェニル－オキセタン、３－（アクリロイルオキシメチル）－２－フェニル－オキセタン、２－（メタクリロイルオキシメチル）オキセタン、２－（アクリロイルオキシメチル）オキセタン、２－（メタクリロイルオキシメチル）－４－トリフロロメチルオキセタン、２－（アクリロイルオキシメチル）－４－トリフロロメチルオキセタンが好ましく、３－（メタクリロイルオキシメチル）－３－エチル－オキセタン、３－（アクリロイルオキシメチル）－３－エチル－オキセタン等が好ましく用いられる。 Examples of the unsaturated compound having a radical polymerizable property and further having an oxetane group include a (meth) acrylic acid ester having an oxetane group. Among such monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl)- 3-Ethyl-oxetan, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetan, 3- (Acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2-( Acryloyloxymethyl) -4-trifluoromethyloxetane is preferable, and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane and the like are preferably used.
　ラジカル重合性を有し、さらにビニル基を有するモノマーとしては、アクリル酸２－（２－ビニロキシエトキシ）エチル、メタクリル酸２－（２－ビニロキシエトキシ）エチル等が挙げられる。 Examples of the monomer having radical polymerization property and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate and the like.
　ラジカル重合性を有し、さらにブロックイソシアネート基を有するモノマーとしては、メタクリル酸２－（０－（１’－メチルプロピリデンアミノ）カルボキシアミノ）エチル、メタクリル酸２－（３，５－ジメチルピラゾリル）カルボニルアミノ）エチル等が挙げられる。 Examples of the monomer having a radical polymerizable property and a blocked isocyanate group include 2- (0- (1'-methylpropyridaneamino) carboxyamino) ethyl methacrylate and 2- (3,5-dimethylpyrazolyl) methacrylate. Carbonylamino) ethyl and the like can be mentioned.
　本発明の感光性樹脂組成物が（Ｚ２）を満足する場合、ラジカル重合性を有し、Ｎ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の自己架橋性基及びＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の架橋性基から選ばれる少なくとも１種の基を有する不飽和化合物から誘導される構成単位を、（Ａ）成分のアルカリ可溶性樹脂が有する全ての繰り返し単位の合計に基づいて、好ましくは１０質量％乃至７０質量％、特に好ましくは２０質量％乃至６０質量％含有する。この構成単位が１０質量％未満の場合は得られる硬化膜の耐熱性や表面硬度が低下する傾向にあり、一方この構成単位の量が７０質量％を超える場合は感光性樹脂組成物の保存安定性が低下する傾向にある。 When the photosensitive resin composition of the present invention satisfies (Z2), it has radical polymerizable properties, and has N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group and block. Non having at least one group selected from self-crosslinking groups such as isocyanate groups and cross-linking groups such as N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group and blocked isocyanate group. The constituent units derived from the saturated compound are preferably 10% by mass to 70% by mass, particularly preferably 20% by mass to 60% by mass, based on the total of all the repeating units of the alkali-soluble resin of the component (A). contains. When this structural unit is less than 10% by mass, the heat resistance and surface hardness of the obtained cured film tend to decrease, while when the amount of this structural unit exceeds 70% by mass, the photosensitive resin composition is stable in storage. The sex tends to decrease.
　また、本発明においては、（Ａ）成分のアクリル重合体は、上述のモノマー以外のモノマー（以下、その他モノマーと称す。）をも構成単位として形成された共重合体であってもよい。その他モノマーは、具体的には、上記カルボキシル基を有するモノマー及びフェノール性ヒドロキシ基を有するモノマーからなる群から選択される少なくとも一種と共重合可能なものであればよく、（Ａ）成分の特性を損ねない限り、特に限定されるものでない。そのようなモノマーの具体例としては、アクリル酸エステル化合物、メタクリル酸エステル化合物、マレイミド、アクリルアミド化合物、アクリロニトリル、スチレン化合物及びビニル化合物等が挙げられる。
　以下、当該その他モノマーの具体例を挙げるが、これらに限定されるものではない。 Further, in the present invention, the acrylic polymer of the component (A) may be a copolymer formed by a monomer other than the above-mentioned monomer (hereinafter, referred to as other monomer) as a constituent unit. Specifically, the other monomer may be a monomer copolymerizable with at least one selected from the group consisting of the above-mentioned monomer having a carboxyl group and the monomer having a phenolic hydroxy group, and has the characteristics of the component (A). It is not particularly limited as long as it does not impair. Specific examples of such monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimides, acrylamide compounds, acrylonitrile, styrene compounds, vinyl compounds and the like.
Specific examples of the other monomers will be given below, but the present invention is not limited thereto.
　前記アクリル酸エステル化合物としては、例えば、メチルアクリレート、エチルアクリレート、イソプロピルアクリレート、ベンジルアクリレート、ナフチルアクリレート、アントリルアクリレート、アントリルメチルアクリレート、フェニルアクリレート、グリシジルアクリレート、フェノキシエチルアクリレート、２，２，２－トリフルオロエチルアクリレート、ｔｅｒｔ－ブチルアクリレート、シクロヘキシルアクリレート、イソボルニルアクリレート、２－メトキシエチルアクリレート、メトキシトリエチレングリコールアクリレート、２－エトキシエチルアクリレート、２－アミノエチルアクリレート、テトラヒドロフルフリルアクリレート、３－メトキシブチルアクリレート、２－メチル－２－アダマンチルアクリレート、２－プロピル－２－アダマンチルアクリレート、８－メチル－８－トリシクロデシルアクリレート、８－エチル－８－トリシクロデシルアクリレート、ジエチレングリコールモノアクリレート、カプロラクトン２－（アクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルアクリレート等が挙げられる。 Examples of the acrylic acid ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-. Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone 2- Examples thereof include (acryloyloxy) ethyl ester and poly (ethylene glycol) ethyl ether acrylate.
　前記メタクリル酸エステル化合物としては、例えば、メチルメタクリレート、エチルメタクリレート、イソプロピルメタクリレート、ベンジルメタクリレート、ナフチルメタクリレート、アントリルメタクリレート、アントリルメチルメタクリレート、フェニルメタクリレート、グリシジルメタクリレート、フェノキシエチルメタクリレート、２，２，２－トリフルオロエチルメタクリレート、ｔｅｒｔ－ブチルメタクリレート、シクロヘキシルメタクリレート、イソボルニルメタクリレート、２－メトキシエチルメタクリレート、メトキシトリエチレングリコールメタクリレート、２－エトキシエチルメタクリレート、２－アミノメチルメタクリレート、テトラヒドロフルフリルメタクリレート、３－メトキシブチルメタクリレート、２－メチル－２－アダマンチルメタクリレート、γ－ブチロラクトンメタクリレート、２－プロピル－２－アダマンチルメタクリレート、８－メチル－８－トリシクロデシルメタクリレート、８－エチル－８－トリシクロデシルメタクリレート、ジエチレングリコールモノメタクリレート、カプロラクトン２－（メタクリロイルオキシ）エチルエステル、ポリ（エチレングリコール）エチルエーテルメタクリレート等が挙げられる。 Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-. Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol mono Examples thereof include methacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate and the like.
　前記アクリルアミド化合物としては、例えば、Ｎ－メチルアクリルアミド、Ｎ－メチルメタクリルアミド、Ｎ，Ｎ－ジメチルアクリルアミド、Ｎ，Ｎ－ジメチルメタクリルアミド、Ｎ－メトキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－ブトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等が挙げられる。 Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples thereof include methyl acrylamide and N-butoxymethylmethacrylamide.
　前記ビニル化合物としては、例えば、メチルビニルエーテル、ベンジルビニルエーテル、シクロヘキシルビニルエーテル、ビニルナフタレン、ビニルアントラセン、ビニルカルバゾール、アリルグリシジルエーテル、３－エテニル－７－オキサビシクロ［４．１．０］ヘプタン、１，２－エポキシ－５－ヘキセン、及び１，７－オクタジエンモノエポキサイド等が挙げられる。 Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allylglycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2. -Epoxy-5-hexene, 1,7-octadiene monoepoxyside and the like.
　前記スチレン化合物としては、ヒドロキシ基を有しないスチレン、例えば、スチレン、α－メチルスチレン、クロロスチレン、ブロモスチレン等が挙げられる。 Examples of the styrene compound include styrene having no hydroxy group, for example, styrene, α-methylstyrene, chlorostyrene, bromostyrene and the like.
　（Ａ）成分であるアルカリ可溶性樹脂の製造において、上記その他モノマーの比率は８０質量％以下であることが好ましく、より好ましくは５０質量％以下であり、さらに好ましくは２０質量％以下である。８０質量％よりも多くなると相対的に必須成分が減るため、本発明の効果を十分に得ることが困難になる。 In the production of the alkali-soluble resin as the component (A), the ratio of the other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and further preferably 20% by mass or less. If it is more than 80% by mass, the essential components are relatively reduced, so that it becomes difficult to sufficiently obtain the effect of the present invention.
　本発明に用いる（Ａ）成分であるアルカリ可溶性樹脂を得る方法は特に限定されないが、例えば、カルボキシル基、フェノール性ヒドロキシ基、及び、熱又は酸の作用によりカルボン酸又はフェノール性ヒドロキシ基を生成する基からなる群から選択される少なくとも一種を有するモノマー、ヒドロキシアルキル基を有するモノマー、所望によりＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、オキセタン基、ビニル基及びブロックイソシアネート基等の自己架橋性基及びＮ－アルコキシメチル基、Ｎ－ヒドロキシメチル基、アルコキシシリル基、エポキシ基、ビニル基、ブロックイソシアネート基等の架橋性基から選ばれる少なくとも１種の基を有するモノマー、所望によりそれ以外の共重合可能なモノマー及び所望により重合開始剤等を共存させた溶剤中において、５０℃乃至１１０℃の温度下で重合反応させることにより、得られる。その際、用いられる溶剤は、アルカリ可溶性樹脂を構成するモノマー及び特定官能基を有するアクリル重合体を溶解するものであれば特に限定されない。具体例としては、後述する（Ｃ）成分に記載する溶剤が挙げられる。 The method for obtaining the alkali-soluble resin which is the component (A) used in the present invention is not particularly limited, but for example, a carboxyl group, a phenolic hydroxy group, and a carboxylic acid or a phenolic hydroxy group are generated by the action of heat or acid. A monomer having at least one selected from the group consisting of groups, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group and a blocked isocyanate. A monomer having at least one group selected from a self-crosslinking group such as a group and a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group and a blocked isocyanate group. It can be obtained by carrying out a polymerization reaction at a temperature of 50 ° C. to 110 ° C. in a solvent in which other copolymerizable monomers and a polymerization initiator and the like coexist if desired. At that time, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble resin and the acrylic polymer having a specific functional group. Specific examples include the solvent described in the component (C) described later.
　このようにして得られる特定官能基を有するアクリル重合体は、通常、溶剤に溶解した溶液の状態である。 The acrylic polymer having a specific functional group thus obtained is usually in the state of a solution dissolved in a solvent.
　また、上記のようにして得られた特定共重合体の溶液を、ジエチルエーテルや水等の撹拌下に投入して再沈殿させ、生成した沈殿物を濾過・洗浄した後、常圧又は減圧下で、常温あるいは加熱乾燥することで、特定共重合体の粉体とすることができる。このような操作により、特定共重合体と共存する重合開始剤や未反応モノマーを除去することができ、その結果、精製した特定共重合体の粉体を得られる。一度の操作で充分に精製できない場合は、得られた粉体を溶剤に再溶解して、上記の操作を繰り返し行えば良い。
　本発明においては、上記特定共重合体の粉体をそのまま用いても良く、あるいはその粉体を、たとえば後述する（Ｃ）成分に再溶解して溶液の状態として用いても良い。 Further, the solution of the specific copolymer obtained as described above is added under stirring with diethyl ether, water or the like to reprecipitate, and the generated precipitate is filtered and washed, and then under normal pressure or reduced pressure. Then, the powder of the specific copolymer can be obtained by drying at room temperature or by heating. By such an operation, the polymerization initiator and the unreacted monomer coexisting with the specific copolymer can be removed, and as a result, the purified powder of the specific copolymer can be obtained. If the powder cannot be sufficiently purified by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the specific copolymer may be used as it is, or the powder may be redissolved in, for example, the component (C) described later and used as a solution.
　また、（Ａ）成分のアルカリ可溶性樹脂としては、ポリアミド酸、ポリアミド酸エステル、一部イミド化したポリアミド酸等のポリイミド前駆体、カルボン酸基含有ポリイミド等のポリイミドを用いることもでき、それらはアルカリ可溶性であれば特にその種類を限定されずに用いることができる。 Further, as the alkali-soluble resin of the component (A), a polyimide precursor such as a polyamic acid, a polyamic acid ester, a partially imidized polyamic acid, or a polyimide such as a carboxylic acid group-containing polyimide can be used, and these are alkali. As long as it is soluble, the type can be used without particular limitation.
　ポリイミド前駆体である前記ポリアミド酸は、一般的に（ｉ）テトラカルボン酸二無水物化合物と（ｊ）ジアミン化合物とを重縮合して得ることができる。 The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensing (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.
　上記（ｉ）テトラカルボン酸二無水物化合物は特に限定はなく、具体例として、ピロメリット酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物などの芳香族テトラカルボン酸、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、１，２，３，４－シクロヘキサンテトラカルボン酸二無水物、３，４－ジカルボキシ－１，２，３，４－テトラヒドロ－１－ナフタレンコハク酸二無水物のような脂環式テトラカルボン酸二無水物、１，２，３，４－ブタンテトラカルボン酸二無水物のような脂肪族テトラカルボン酸二無水物を挙げることができる。
　これらは、１種単独で用いてもよく、又は２種以上の化合物を組み合わせて用いてもよい。 The above (i) tetracarboxylic dianhydride compound is not particularly limited, and as specific examples, pyromellitic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 3,3'. , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenyl ethertetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride Such as aromatic tetracarboxylic acids, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetra Alicyclic tetracarboxylic dianhydride, 1,2,3, such as carboxylic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalensuccinic dianhydride, Examples thereof include aliphatic tetracarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride.
These may be used individually by 1 type, or may be used in combination of 2 or more types.
　また、上記（ｊ）ジアミン化合物も特に限定されることはなく、例えば、２，４－ジアミノ安息香酸、２，５－ジアミノ安息香酸、３，５－ジアミノ安息香酸、４，６－ジアミノ－１，３－ベンゼンジカルボン酸、２，５－ジアミノ－１，４－ベンゼンジカルボン酸、ビス（４－アミノ－３－カルボキシフェニル）エーテル、ビス（４－アミノ－３，５－ジカルボキシフェニル）エーテル、ビス（４－アミノ－３－カルボキシフェニル）スルホン、ビス（４－アミノ－３，５－ジカルボキシフェニル）スルホン、４，４’－ジアミノ－３，３’－ジカルボキシビフェニル、４，４’－ジアミノ－３，３’－ジカルボキシ－５，５’－ジメチルビフェニル、４，４’－ジアミノ－３，３’－ジカルボキシ－５，５’－ジメトキシビフェニル、１，４－ビス（４－アミノ－３－カルボキシフェノキシ）ベンゼン、１，３－ビス（４－アミノ－３－カルボキシフェノキシ）ベンゼン、ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］スルホン、ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノ－３－カルボキシフェノキシ）フェニル］ヘキサフルオロプロパン、２，４－ジアミノフェノール、３，５－ジアミノフェノール、２，５－ジアミノフェノール、４，６－ジアミノレゾルシノール、２，５－ジアミノハイドロキノン、ビス（３－アミノ－４－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３，５－ジヒドロキシフェニル）エーテル、ビス（３－アミノ－４－ヒドロキシフェニル）メタン、ビス（４－アミノ－３－ヒドロキシフェニル）メタン、ビス（４－アミノ－３，５－ジヒドロキシフェニル）メタン、ビス（３－アミノ－４－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３－ヒドロキシフェニル）スルホン、ビス（４－アミノ－３，５－ジヒドロキシフェニル）スルホン、２，２－ビス（３－アミノ－４－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３－ヒドロキシフェニル）ヘキサフルオロプロパン、２，２－ビス（４－アミノ－３，５－ジヒドロキシフェニル）ヘキサフルオロプロパン、４，４’－ジアミノ－３，３’－ジヒドロキシビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－５，５’－ジメチルビフェニル、４，４’－ジアミノ－３，３’－ジヒドロキシ－５，５’－ジメトキシビフェニル、１，４－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゼン、１，３－ビス（３－アミノ－４－ヒドロキシフェノキシ）ベンゼン、１，４－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゼン、１，３－ビス（４－アミノ－３－ヒドロキシフェノキシ）ベンゼン、ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］スルホン、ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－アミノ－４－ヒドロキシフェノキシ）フェニル］ヘキサフルオロプロパン等フェノール性ヒドロキシ基を有するジアミン化合物、１，３－ジアミノ－４－メルカプトベンゼン、１，３－ジアミノ－５－メルカプトベンゼン、１，４－ジアミノ－２－メルカプトベンゼン、ビス（４－アミノ－３－メルカプトフェニル）エーテル、２，２－ビス（３－アミノ－４－メルカプトフェニル）ヘキサフルオロプロパン等チオフェノール基を有するジアミン化合物、１，３－ジアミノベンゼン－４－スルホン酸、１，３－ジアミノベンゼン－５－スルホン酸、１，４－ジアミノベンゼン－２－スルホン酸、ビス（４－アミノベンゼン－３－スルホン酸）エーテル、４，４’－ジアミノビフェニル－３，３’－ジスルホン酸、４，４’－ジアミノ－３，３’－ジメチルビフェニル－６，６’－ジスルホン酸等スルホン酸基を有するジアミン化合物が挙げられる。また、ｐ－フェニレンジアミン、ｍ－フェニレンジアミン、４，４’－メチレン－ビス（２，６－エチルアニリン）、４，４’－メチレン－ビス（２－イソプロピル－６－メチルアニリン）、４，４’－メチレン－ビス（２，６－ジイソプロピルアニリン）、２，４，６－トリメチル－１，３－フェニレンジアミン、２，３，５，６－テトラメチル－１，４－フェニレンジアミン、ｏ－トリジン、ｍ－トリジン、３，３’，５，５’－テトラメチルベンジジン、ビス［４－（３－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（３－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、４，４’－ジアミノ－３，３’－ジメチルジシクロヘキシルメタン、４，４’－ジアミノジフェニルエーテル、３，４－ジアミノジフェニルエーテル、４，４’－ジアミノジフェニルメタン、２，２－ビス（４－アニリノ）ヘキサフルオロプロパン、２，２－ビス（３－アニリノ）ヘキサフルオロプロパン、２，２－ビス（３－アミノ－４－トルイル）ヘキサフルオロプロパン、１，４－ビス（４－アミノフェノキシ）ベンゼン、１，３－ビス（４－アミノフェノキシ）ベンゼン、ビス［４－（４－アミノフェノキシ）フェニル］スルホン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］プロパン、２，２－ビス［４－（４－アミノフェノキシ）フェニル］ヘキサフルオロプロパン、２，２’－ビス（トリフルオロメチル）ベンジジン等のジアミン化合物を挙げることが出来る。
　これらは、１種単独で用いてもよく、又は２種以上の化合物を組み合わせて用いてもよい。 The diamine compound (j) is also not particularly limited, and for example, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1. , 3-Benzene dicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxyphenyl) ether, Bis (4-amino-3-carboxyphenyl) sulfone, Bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis (4-amino) -3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxyphenoxy) phenyl] sulfone, bis [4- (4- (4- (4-) 4-) Amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-Diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-) Amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) Methan, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3) -Amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl Le, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino) -4-Hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino) -4-Hydroxyphenoxy) phenyl] sulfonate, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoro Diamine compounds having a phenolic hydroxy group such as propane, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-) Diamine compounds having a thiophenol group such as 3-mercaptophenyl) ether, 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane, 1,3-diaminobenzene-4-sulfonic acid, 1,3- Diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, Examples thereof include diamine compounds having a sulfonic acid group such as 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis (2,6-ethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline), 4, 4'-Methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Trizine, m-trizine, 3,3', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (3-aminophenoxy) phenyl] Propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoropropane, 2,2-bis (3-anilino) hexafluoropropane, 2,2-bis (3-amino-4) -Truyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2 Diamines such as -bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine Compounds can be mentioned.
These may be used individually by 1 type, or may be used in combination of 2 or more types.
　本発明で用いられるポリアミド酸が（ｉ）テトラカルボン酸二無水物化合物と（ｊ）ジアミン化合物から製造される場合、両化合物の配合比、すなわち（ｊ）ジアミン化合物の総モル数／（ｉ）テトラカルボン酸二無水物化合物の総モル数は０．７乃至１．２であることが望ましい。通常の重縮合反応同様、このモル比が１に近いほど生成するポリアミド酸の重合度は大きくなり分子量が増加する。 When the polyamic acid used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the compounding ratio of both compounds, that is, (j) the total number of moles of the diamine compound / (i). The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1, the greater the degree of polymerization of the polyamic acid produced and the higher the molecular weight.
　また、ジアミン化合物を過剰に用いて重合した際、残存するポリアミド酸の末端アミノ基に対してカルボン酸無水物を反応させ末端アミノ基を保護することもできる。
　このようなカルボン酸無水物の例としてはフタル酸無水物、トリメリット酸無水物、無水マレイン酸、ナフタル酸無水物、水素化フタル酸無水物、メチル－５－ノルボルネン－２，３－ジカルボン酸無水物、無水イタコン酸、テトラヒドロフタル酸無水物等を挙げることができる。 Further, when the diamine compound is excessively used for polymerization, the carboxylic acid anhydride can be reacted with the terminal amino group of the remaining polyamic acid to protect the terminal amino group.
Examples of such carboxylic acid anhydrides are phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydride phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic acid. Anhydride, itaconic anhydride, tetrahydrophthalic anhydride and the like can be mentioned.
　ポリアミド酸の製造において、ジアミン化合物とテトラカルボン酸二無水物化合物との反応の反応温度は－２０℃乃至１５０℃、好ましくは－５℃乃至１００℃の任意の温度を選択することができる。高分子量のポリアミド酸を得るには、反応温度５℃乃至４０℃、反応時間１時間乃至４８時間の範囲にて適宜選択する。低分子量で保存安定性の高く部分的にイミド化されたポリアミド酸を得るには反応温度４０℃乃至９０℃、反応時間１０時間以上から選択することがより好ましい。
　また、末端アミノ基を酸無水物で保護する場合の反応温度は－２０℃乃至１５０℃、好ましくは－５℃乃至１００℃の任意の温度を選択することができる。 In the production of the polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C. In order to obtain a high molecular weight polyamic acid, a reaction temperature of 5 ° C. to 40 ° C. and a reaction time of 1 hour to 48 hours are appropriately selected. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select from a reaction temperature of 40 ° C. to 90 ° C. and a reaction time of 10 hours or more.
Further, when the terminal amino group is protected with an acid anhydride, the reaction temperature can be selected from −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C.
　ジアミン化合物とテトラカルボン酸二無水物化合物の反応は溶剤中で行なうことができる。その際に使用できる溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、Ｎ－メチルピロリドン、Ｎ－ビニルピロリドン、Ｎ－メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルスルホキシド、ｍ－クレゾール、γ－ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸エチル、３－メトキシプロピオン酸メチル、２－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、２－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、２－エトキシプロピオン酸エチル、エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、プロピレングリコールジメチルエーテル、ジプロピレングリコールジメチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、カルビトールアセテート、エチルセロソルブアセテート、シクロヘキサノン、メチルエチルケトン、メチルイソブチルケトン、２－ヘプタノン等を挙げることができる。これらは単独でも、混合して使用しても良い。さらに、ポリアミド酸を溶解しない溶剤であっても、重合反応により生成したポリアミド酸が析出しない範囲で、上記溶剤に混合して使用してもよい。 The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, etc. Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 -Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, Examples thereof include methyl isobutyl ketone and 2-heptanone. These may be used alone or in combination. Further, even if the solvent does not dissolve the polyamic acid, it may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.
　このようにして得られたポリアミド酸を含む溶液は、感光性樹脂組成物の調製にそのまま用いることができる。また、ポリアミド酸を水、メタノール、エタノール等の貧溶剤に沈殿単離させて回収して用いることもできる。 The solution containing the polyamic acid thus obtained can be used as it is for the preparation of the photosensitive resin composition. Further, the polyamic acid can be recovered and used by precipitating and isolating it in a poor solvent such as water, methanol or ethanol.
　また、（Ａ）成分としては、任意のポリイミドも用いることができる。本発明に用いるポリイミドとは前記ポリアミド酸などのポリイミド前駆体を化学的又は熱的に５０％以上イミド化させたものである。 Further, any polyimide can be used as the component (A). The polyimide used in the present invention is a polyimide precursor such as the polyamic acid chemically or thermally imidized by 50% or more.
　本発明の感光性樹脂組成物に用いるポリイミドは、アルカリ溶解性を与えるためにカルボキシル基及びフェノール性ヒドロキシ基から選ばれる基を有することが好ましい。
　ポリイミドへのカルボキシル基又はフェノール性ヒドロキシ基の導入方法は、カルボキシル基又はフェノール性ヒドロキシ基を有するモノマーを用いる方法、カルボキシル基又はフェノール性ヒドロキシ基を有する酸無水物でアミン末端を封止する方法、或いは、ポリアミド酸などのポリイミド前駆体をイミド化する際にイミド化率を９９％以下にする方法等が用いられる。 The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
The method for introducing a carboxyl group or a phenolic hydroxy group into the polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of sealing the amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxy group, and a method. Alternatively, a method of reducing the imidization rate to 99% or less when imidizing a polyimide precursor such as polyamic acid is used.
　このようなポリイミドは上述のポリアミド酸などのポリイミド前駆体を合成した後、化学イミド化もしくは熱イミド化を行うことで得ることができる。
　化学イミド化の方法としては一般的にポリイミド前駆体溶液に過剰の無水酢酸およびピリジンを添加し室温から１００℃で反応させる方法が用いられる。また、熱イミド化の方法としては一般的に、ポリイミド前駆体溶液を温度１８０℃乃至２５０℃で脱水しながら過熱する方法が用いられる。 Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid and then performing chemical imidization or thermal imidization.
As a method of chemical imidization, a method of adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100 ° C. is generally used. Further, as a method of thermal imidization, a method of heating a polyimide precursor solution while dehydrating it at a temperature of 180 ° C. to 250 ° C. is generally used.
　また、（Ａ）成分のアルカリ可溶性樹脂としては、さらにフェノールノボラック樹脂を用いることができる。 Further, as the alkali-soluble resin of the component (A), a phenol novolac resin can be further used.
　また、（Ａ）成分のアルカリ可溶性樹脂としては、ポリエステルポリカルボン酸を用いることもできる。ポリエステルポリカルボン酸は、酸二無水物とジオールから、ＷＯ２００９／０５１１８６に記載の方法により、得ることができる。
　酸二無水物としては、上記（ｉ）テトラカルボン酸二無水物が挙げられる。
　ジオールとしては、ビスフェノールＡ、ビスフェノールＦ、４，４’－ジヒドロキシビフェニル、ベンゼン－１，３－ジメタノール、ベンゼン－１，４－ジメタノール等の芳香族ジオール、水添ビスフェノールＡ、水添ビスフェノールＦ、１，４－シクロヘキサンジオール、１，３－シクロヘキサンジメタノール、１，４－シクロヘキサンジメタノール等の脂環族ジオール、及びエチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール等の脂肪族ジオール等が挙げられる。 Further, as the alkali-soluble resin of the component (A), a polyester polycarboxylic acid can also be used. Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO2009 / 051186.
Examples of the acid dianhydride include the above-mentioned (i) tetracarboxylic dianhydride.
Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. , 1,4-Cyclohexanediol, 1,3-Cyclohexanedimethanol, alicyclic diols such as 1,4-cyclohexanedimethanol, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol And the like, aliphatic diols and the like.
　また、本発明においては、（Ａ）成分のアルカリ可溶性樹脂は、複数種のアルカリ可溶性樹脂の混合物であってもよい。 Further, in the present invention, the alkali-soluble resin of the component (A) may be a mixture of a plurality of types of alkali-soluble resins.
＜（Ｂ）成分＞
　本発明の（Ｂ）成分は、フッ素含有熱分解性重合体である。フッ素含有熱分解性重合体は、熱分解性を有し、重合性単量体の重合体構造を有する主鎖（ａ）と、前記一般式（１）で表される官能基を有する側鎖（ｂ）を有することを特徴とする。
　ここで「熱分解性」とは、５０～３００℃のいずれかの環境下に３０分間さらすことにより熱分解することを指す。例えば、カルボキシル基を有する（Ｂ）成分のフッ素含有熱分解性重合体の場合、５０～３００℃の環境下に３０分間さらすことにより、カルボキシル基をブロックした構造が脱離し、カルボキシル基が発生する。　（Ｂ）成分のフッ素含有熱分解性重合体としては、例えば、重合性単量体の重合体構造を有する主鎖と、フッ素化アルキル基および／またはポリ（パーフルオロアルキレンエーテル）鎖を有する側鎖と、前記一般式（１）で表される構造を有する基を有する側鎖とを有するものが挙げられる。 <Ingredient (B)>
The component (B) of the present invention is a fluorine-containing pyrolytic polymer. The fluorine-containing thermally decomposable polymer has a main chain (a) having a thermally decomposable property and a polymer structure of a polymerizable monomer, and a side chain having a functional group represented by the general formula (1). It is characterized by having (b).
Here, "thermally decomposable" means that it is thermally decomposed by being exposed to any environment of 50 to 300 ° C. for 30 minutes. For example, in the case of a fluorine-containing pyrolyzable polymer having a carboxyl group (B), the structure blocking the carboxyl group is removed by exposing it to an environment of 50 to 300 ° C. for 30 minutes, and a carboxyl group is generated. .. Examples of the fluorine-containing pyrolytic polymer of the component (B) include a main chain having a polymer structure of a polymerizable monomer and a side having an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain. Examples thereof include a chain and a side chain having a group having a structure represented by the general formula (1).
　前記一般式（１）で表される官能基を有する側鎖（ｂ）の中でも、Ｒ１、Ｒ２およびＲ３がそれぞれ水素原子または炭素原子数１～１８の有機基である。さらに、Ｒ１、Ｒ２およびＲ３がそれぞれ水素原子のものが好ましい。Ｙ１は酸素原子又は硫黄原子である。 Among the side chains (b) having a functional group represented by the general formula (1), R 1 , R 2 and R 3 are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively. Further, it is preferable that R 1 , R 2 and R 3 are hydrogen atoms, respectively. Y 1 is an oxygen atom or a sulfur atom.
　前記一般式（１）で表される官能基を有する側鎖（ｂ）中でも、Ｒ４はフッ素化アルキル基又はポリ（パーフルオロアルキレンエーテル）鎖である。さらに、フッ素原子が直接結合した炭素原子の数が１～６のフッ素化アルキル基が、優れた平滑性を発現するフッ素含有熱分解性重合体が得られることから好ましく、フッ素原子が直接結合した炭素原子の数が４～６のフッ素化アルキル基がより好ましく、フッ素原子が直接結合した炭素原子の数が６のフッ素化アルキル基が更に好ましい。 Formula side chain having a functional group represented by (1) (b) Among them, R 4 is a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain. Further, a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom is preferable because a fluorine-containing thermally decomposable polymer exhibiting excellent smoothness can be obtained, and the fluorine atom is directly bonded. A fluorinated alkyl group having 4 to 6 carbon atoms is more preferable, and a fluorinated alkyl group having 6 carbon atoms to which a fluorine atom is directly bonded is further preferable.
　前記Ｒ４は、例えば、下記式（Ｒｆ－１）～（Ｒｆ－７）のいずれか１つの基を表す。
Figure JPOXMLDOC01-appb-C000007
 The R 4 represents, for example, any one group of the following formulas (Rf-1) to (Rf-7).
Figure JPOXMLDOC01-appb-C000007
　上記式（Ｒｆ－１）～（Ｒｆ－４）中のｎは、例えば１～６の整数であり、好ましくは４～６の整数である。上記式（Ｒｆ－５）中のｍは、例えば１～１８の整数であり、ｎは０～５の整数であり、かつｍ及びｎの合計は１～２３である。好ましくは、ｍは１～５の整数であり、ｎは０～４の整数であり、かつｍ及びｎの合計は４～５である。上記式（Ｒｆ－６）中のｍは例えば１～６の整数であり、ｎは１～３の整数であり、ｌは１～２０の整数であり、ｐは０～５の整数であり、かつ、ｍ、ｐ及びｎとｌとの積の合計は２～７１である。好ましくは、ｍは１～３の整数であり、ｎは１～３の整数であり、ｌは１～６の整数であり、ｐは０～２の整数であり、かつ、ｍ、ｐ及びｎとｌとの積の合計は２～２３である。
　式（Ｒｆ－６）は、Ｒ４がポリ（パーフルオロアルキレンエーテル）鎖であることを表す。 N in the above formulas (Rf-1) to (Rf-4) is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. In the above formula (Rf-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is 4 to 5. In the above equation (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, and p is an integer of 0 to 5. Moreover, the total product of m, p and n and l is 2 to 71. Preferably, m is an integer of 1 to 3, n is an integer of 1 to 3, l is an integer of 1 to 6, p is an integer of 0 to 2, and m, p and n. The sum of the products of and l is 2 to 23.
The formula (Rf-6) represents that R 4 is a poly (perfluoroalkylene ether) chain.
　Ｒ４の具体的な例として、例えば下記の式（γ１－１）～（γ１－４）等を好ましく例示することができる。
Figure JPOXMLDOC01-appb-C000008
 Specific examples of R 4, for example, the following formula (γ1-1) can be preferably exemplified ~ (γ1-4) or the like.
Figure JPOXMLDOC01-appb-C000008
　式（γ１－１）～式（γ１－３）におけるｎは、例えば、０～５である。また、式（γ１－４）におけるｎは、例えば、０～２０である。 N in the formulas (γ1-1) to (γ1-3) is, for example, 0 to 5. Further, n in the formula (γ1-4) is, for example, 0 to 20.
　前記好ましい側鎖（ｂ）としては、例えば、下記に示す側鎖等を好ましく例示することができる。これらの中でも、式（１－１）で表されるものが、工業的に入手可能な原料を用いて得られること、表面自由エネルギーが低いため優れた平滑性を発現するフッ素含有熱分解性重合体が合成しやすいことから好ましい。 As the preferable side chain (b), for example, the side chain shown below can be preferably exemplified. Among these, the one represented by the formula (1-1) is obtained by using an industrially available raw material, and has a low surface free energy, so that it exhibits excellent smoothness. It is preferable because the coalescence is easy to synthesize.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　本発明のフッ素含有熱分解性重合体は、本発明の効果を損なわない範囲で前記一般式（１）以外の側鎖（ｂ’）を含有していても良い。前記側鎖（ｂ’）としては、例えば、下記一般式（１’）で表される側鎖を例示することができる。 The fluorine-containing pyrolytic polymer of the present invention may contain a side chain (b') other than the general formula (1) as long as the effect of the present invention is not impaired. As the side chain (b'), for example, a side chain represented by the following general formula (1') can be exemplified.
Figure JPOXMLDOC01-appb-C000010
 （式中、Ｒ１１、Ｒ２１及びＲ３１はそれぞれ水素原子または炭素原子数１～１８の有機基、Ｒ４１は炭素原子数１～１８の有機基であって、Ｒ３１とＲ４１はたがいに結合してＹ１１をヘテロ原子とする複素環を形成していてもよく、Ｙ１１は酸素原子又は硫黄原子である。）
Figure JPOXMLDOC01-appb-C000010
 (In the formula, R 11 , R 21 and R 31 are hydrogen atoms or organic groups having 1 to 18 carbon atoms, respectively, R 41 is an organic group having 1 to 18 carbon atoms, and R 31 and R 41 are paired with each other. It may be bonded to to form a heterocycle having Y 11 as a hetero atom, and Y 11 is an oxygen atom or a sulfur atom.)
　前記一般式（１’）で表される官能基を有する側鎖（ｂ’）の中でも、Ｒ１１、Ｒ２１およびＲ３１がそれぞれ水素原子で、Ｒ４１が炭素原子数１～１８の有機基で、Ｙ１が酸素原子または硫黄原子であるものが、ブロック化されたカルボキシル基と復活したカルボキシル基の極性の差が大きく、塗膜の平滑性とリコート性との両立が可能となるレジスト膜やカラーフィルタ保護膜等の硬化塗膜が得られるフッ素含有熱分解性重合体が得られることから好ましく、下記式（１’－１）で表される側鎖がより好ましい。 Among the side chains (b') having a functional group represented by the general formula (1'), R 11 , R 21 and R 31 are hydrogen atoms, respectively, and R 41 is an organic group having 1 to 18 carbon atoms. A resist film in which Y 1 is an oxygen atom or a sulfur atom has a large difference in polarity between the blocked carboxyl group and the revived carboxyl group, and can achieve both smoothness and recoatability of the coating film. It is preferable because a fluorine-containing thermally decomposable polymer that can obtain a cured coating film such as a color filter protective film is obtained, and a side chain represented by the following formula (1'-1) is more preferable.
　フッ素含有熱分解性重合体は市販されているものを用いてもよく、重合性単量体の重合体構造を有する主鎖と、フッ素化アルキル基および／またはポリ（パーフルオロアルキレンエーテル）鎖を有する側鎖と、前記一般式（１）で表される構造を有する基を有する側鎖とを有するものとして例えば、ＤＳ－２１（ＤＩＣ株式会社製）を挙げることができる。 As the fluorine-containing pyrolytic polymer, a commercially available one may be used, and a main chain having a polymer structure of a polymerizable monomer and an alkyl fluorinated group and / or a poly (perfluoroalkylene ether) chain are used. DS-21 (manufactured by DIC Co., Ltd.) can be mentioned as an example having a side chain having a side chain and a side chain having a group having a structure represented by the general formula (1).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　本発明において、前記アルカリ可溶性樹脂１００質量部に対して、好ましくは０．０１質量部乃至１０質量部、より好ましくは０．０１質量部乃至１質量部のフッ素含有熱分解性重合体を含有する。 In the present invention, the fluorine-containing pyrolytic polymer is preferably contained in an amount of 0.01 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 1 part by mass with respect to 100 parts by mass of the alkali-soluble resin. ..
＜（Ｃ）成分＞
　本発明に用いる（Ｃ）成分は、溶剤として、（Ａ）成分、（Ｂ）成分、及び必要に応じて後述の（Ｄ）成分、（Ｅ）成分を溶解し、且つ所望により添加される後述のその他添加剤などを溶解するものであり、斯様な溶解能を有する溶剤であれば、その種類及び構造などは特に限定されるものでない。 <Component (C)>
The component (C) used in the present invention dissolves the component (A), the component (B), and if necessary, the components (D) and (E) described below as a solvent, and is added as desired. The type and structure of the solvent are not particularly limited as long as the solvent dissolves other additives and the like and has such a dissolving ability.
　斯様な（Ｃ）成分としては、例えば、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、メチルセロソルブアセテート、エチルセロソルブアセテート、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコール、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテル、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２－ヘプタノン、γ―ブチロラクトン、２－ヒドロキシプロピオン酸エチル、２－ヒドロキシ－２－メチルプロピオン酸エチル、エトキシ酢酸エチル、ヒドロキシ酢酸エチル、２－ヒドロキシ－３－メチルブタン酸メチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、乳酸エチル、乳酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドン等が挙げられる。 Examples of such component (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, and propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone , 2-Hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , Ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, and Examples thereof include N-methylpyrrolidone.
　これらの溶剤は、一種単独で、または二種以上の組合せで使用することができる。
　これら（Ｃ）成分の中、下層膜を溶解させない点からヒドロキシ基を有しない溶媒、すなわち、メチルセロソルブアセテート、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールプロピルエーテルアセテート、トルエン、キシレン、メチルエチルケトン、シクロペンタノン、シクロヘキサノン、２－ブタノン、３－メチル－２－ペンタノン、２－ペンタノン、２－ヘプタノン、γ―ブチロラクトン、エトキシ酢酸エチル、３－メトキシプロピオン酸メチル、３－メトキシプロピオン酸エチル、３－エトキシプロピオン酸エチル、３－エトキシプロピオン酸メチル、ピルビン酸メチル、ピルビン酸エチル、酢酸エチル、酢酸ブチル、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、及びＮ－メチルピロリドン等が好ましい。これら溶剤は、一般にフォトレジスト材料のための溶剤として用いられている。
ヒドロキシ基を有する溶剤を用いる場合は、上述した通り下層膜を溶解させない点からヒドロキシ基を有しない溶剤と組み合わせて使用することが好ましい。組み合わせる溶媒は塗膜性が良好で下層膜を溶解させなければ一種類でも二種類以上でも特に限定はされない。この場合、下層膜を溶解させない観点からヒドロキシ基を有する溶剤の量は（Ｃ）成分全体に対して７０重量％以下が好ましく、６０重量％以下がより好ましく、５０重量％以下が更に好ましく、３０重量％以下が最も好ましい。 These solvents can be used alone or in combination of two or more.
Among these components (C), solvents having no hydroxy group from the viewpoint of not dissolving the lower layer film, that is, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, Cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3- Ethyl ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are preferred. These solvents are generally used as solvents for photoresist materials.
When a solvent having a hydroxy group is used, it is preferable to use it in combination with a solvent having no hydroxy group from the viewpoint of not dissolving the lower layer film as described above. The solvent to be combined is not particularly limited to one type or two or more types as long as the coating film property is good and the underlying film is not dissolved. In this case, the amount of the solvent having a hydroxy group is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less, and 30% by weight, based on the whole component (C) from the viewpoint of not dissolving the underlayer film. Most preferably, it is by weight or less.
＜（Ｄ）成分＞
　（Ｄ）成分である感光剤としては、（Ｄ－１）１，２－キノンジアジド化合物、（Ｄ－２）光ラジカル発生剤、（Ｄ－３）光酸発生剤が挙げられる。 <Component (D)>
Examples of the photosensitizer as the component (D) include (D-1) 1,2-quinonediazide compound, (D-2) photoradical generator, and (D-3) photoacid generator.
　（Ｄ－１）１，２－キノンジアジド化合物としては、ヒドロキシ基又はアミノ基のいずれか一方か、ヒドロキシ基及びアミノ基の両方を有する化合物であって、これらのヒドロキシ基又はアミノ基（ヒドロキシ基とアミノ基の両方を有する場合は、それらの合計量）のうち、好ましくは１０モル％乃至１００モル％、特に好ましくは２０モル％乃至９５モル％が１，２－キノンジアジドスルホン酸でエステル化、またはアミド化された化合物を用いることができる。
　上記１，２－キノンジアジドスルホン酸としては、例えば１，２－ナフトキノン－２－ジアジド－５－スルホン酸、１，２－ナフトキノン－２－ジアジド－４－スルホン酸、１，２－ベンゾキノン－２－ジアジド－４－スルホン酸等が挙げられ、前述のヒドロキシ基又はアミノ基のいずれか一方あるいは両方を有する化合物との反応では、該１，２－キノンジアジドスルホン酸の塩化物を用いることができる。
　上記（Ｄ－１）１，２－キノンジアジド化合物としては、ジアゾナフトキノンを用いることができる。 (D-1) The 1,2-quinonediazide compound is a compound having either a hydroxy group or an amino group, or both a hydroxy group and an amino group, and these hydroxy groups or amino groups (with a hydroxy group). Of the total amount of both amino groups, preferably 10 mol% to 100 mol%, particularly preferably 20 mol% to 95 mol%, esterified with 1,2-quinonediazide sulfonic acid, or Amidated compounds can be used.
Examples of the 1,2-quinone diazido sulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-. Examples thereof include diazido-4-sulfonic acid, and the chloride of 1,2-quinonediazide sulfonic acid can be used in the reaction with the above-mentioned compound having either one or both of a hydroxy group and an amino group.
Diazonaphthoquinone can be used as the (D-1) 1,2-quinone diazide compound.
　前記ヒドロキシ基を有する化合物としては例えば、フェノール、ｏ－クレゾール、ｍ－クレゾール、ｐ－クレゾール、ハイドロキノン、レゾルシノール、カテコール、ガリック酸メチル、ガリック酸エチル、１，３，３－トリス（４－ヒドロキシフェニル）ブタン、４，４－イソプロプリデンジフェノール、２，２－ビス（４－ヒドロキシフェニル）プロパン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン、４，４’－ジヒドロキシフェニルスルホン、４，４－ヘキサフルオロイソプロピリデンジフェノール、４，４’，４’’―トリスヒドロキシフェニルエタン、１，１，１－トリスヒドロキシフェニルエタン、４，４’－［１－［４－［１－（４－ヒドロキシフェニル）－１－メチルエチル］フェニル］エチリデン］ビスフェノール、２，４－ジヒドロキシベンゾフェノン、２，３，４－トリヒドロキシベンゾフェノン、２，２’，４，４’－テトラヒドロキシベンゾフェノン、２，３，４，４’－テトラヒドロキシベンゾフェノン、２，２’，３，４，４’－ペンタヒドロキシベンゾフェノン、２，５－ビス（２－ヒドロキシ－５－メチルベンジル）メチルなどのフェノール化合物、エタノール、２－プロパノール、４－ブタノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、２－メトキシエタノール、２－ブトキシエタノール、２－メトキシプロパノール、２－ブトキシプロパノール、乳酸エチル、乳酸ブチルなどの脂肪族アルコール類を挙げることができる。 Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallicate, ethyl gallicate, and 1,3,3-tris (4-hydroxyphenyl). ) Butane, 4,4-isopropridendiphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4 -Hexafluoroisopropyridene diphenol, 4,4', 4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1- [4- [1- (4- (4- (4- (4-) Hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2,3 Phenol compounds such as 4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone, 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2- Hydroxyl groups such as propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate. Alcohols can be mentioned.
　また、前記アミノ基を含有する化合物としては、アニリン、ｏ－トルイジン、ｍ－トルイジン、ｐ－トルイジン、４－アミノジフェニルメタン、４－アミノジフェニル、ｏ－フェニレンジアミン、ｍ－フェニレンジアミン、ｐ－フェニレンジアミン、４，４’－ジアミノフェニルメタン、４，４’－ジアミノジフェニルエーテル、などのアニリン類、アミノシクロヘキサンを挙げることができる。 Examples of the amino group-containing compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine. , 4,4'-Diaminophenylmethane, 4,4'-diaminodiphenyl ether, and other anilines, aminocyclohexane can be mentioned.
　さらに、ヒドロキシ基とアミノ基両方を含有する化合物としては、例えば、ｏ－アミノフェノール、ｍ－アミノフェノール、ｐ－アミノフェノール、４－アミノレゾルシノール、２，３－ジアミノフェノール、２，４－ジアミノフェノール、４，４’－ジアミノ－４’’－ヒドロキシトリフェニルメタン、４－アミノ－４’，４’’－ジヒドロキシトリフェニルメタン、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）エーテル、ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）メタン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）プロパン、２，２－ビス（４－アミノ－３－カルボキシ－５－ヒドロキシフェニル）ヘキサフルオロプロパンなどのアミノフェノール類、２－アミノエタノール、３－アミノプロパノール、４－アミノシクロヘキサノールなどのアルカノールアミン類を挙げることができる。 Further, examples of the compound containing both a hydroxy group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, and 2,4-diaminophenol. , 4,4'-Diamino-4''-hydroxytriphenylmethane, 4-amino-4', 4''-dihydroxytriphenylmethane, bis (4-amino-3-carboxy-5-hydroxyphenyl) ether, Bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-3) Aminophenols such as carboxy-5-hydroxyphenyl) hexafluoropropane and alkanolamines such as 2-aminoethanol, 3-aminopropanol and 4-aminocyclohexanol can be mentioned.
　これらの１，２－キノンジアジド化合物は単独または２種以上の組み合わせで使用することができる。 These 1,2-quinonediazide compounds can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物がポジ型感光性樹脂組成物である場合に（Ｄ－１）成分のキノンジアジド基を有する化合物を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、好ましくは５質量部乃至１００質量部、より好ましくは８質量部乃至５０質量部、更に好ましくは１０質量部乃至４０質量部である。５質量部未満の場合、ポジ型感光性樹脂組成物の露光部と未露光部の現像液への溶解速度差が小さくなり、現像によるパターニングが困難である場合がある。また、１００質量部を超えると、短時間での露光で１，２－キノンジアジド化合物が十分に分解されないため感度が低下する場合や、（Ｄ－１）成分が光を吸収してしまい硬化膜の透明性を低下させてしまう場合がある。 When the photosensitive resin composition of the present invention is a positive photosensitive resin composition, the contents when the compound having a quinonediazide group of the component (D-1) is contained are the component (A) and the component (B). It is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 50 parts by mass, and further preferably 10 parts by mass to 40 parts by mass with respect to 100 parts by mass in total. If it is less than 5 parts by mass, the difference in dissolution rate between the exposed portion and the unexposed portion of the positive photosensitive resin composition in the developing solution becomes small, and patterning by development may be difficult. On the other hand, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed by exposure in a short time, so that the sensitivity is lowered, or the component (D-1) absorbs light and the cured film. It may reduce transparency.
　（Ｄ－２）光ラジカル発生剤は、露光によりラジカルを発生するものであれば特に制限はない。具体例としては、前述した上層膜形成用組成物中で用いる（Ｄ）成分中に挙げた（Ｄ－２）と同じものが挙げられる。
　具体例としては、例えばベンゾフェノン、ミヒラーケトン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン、４－メトキシ－４’－ジメチルアミノベンゾフェノン、２－エチルアントラキノン、フェナントレン等の芳香族ケトン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインフェニルエーテル等のベンゾインエーテル類、メチルベンゾイン、エチルベンゾイン等のベンゾイン、２－（ｏ－クロロフェニル）－４，５－フェニルイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メトキシフェニル）イミダゾール２量体、２－（ｏ－フルオロフェニル）－４，５－ジフェニルイミダゾール２量体、２－（ｏ－メトキシフェニル）－４，５－ジフェニルイミダゾール２量体、２，４，５－トリアリールイミダゾール２量体、２－（ｏ－クロロフェニル）－４，５－ジ（ｍ－メチルフェニル）イミダゾール２量体、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン、２－トリクロロメチル－５－スチリル－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（ｐ－シアノスチリル）－１，３，４－オキサジアゾール、２－トリクロロメチル－５－（ｐ－メトキシスチリル）－１，３，４－オキサジアゾール等のハロメチルオキサジアゾール化合物、２，４－ビス（トリクロロメチル）－６－ｐ－メトキシスチリル－Ｓ－トリアジン、２，４－ビス（トリクロロメチル）－６－（１－ｐ－ジメチルアミノフェニル－１，３－ブタジエニル）－Ｓ－トリアジン、２－トリクロロメチル－４－アミノ－６－ｐ－メトキシスチリル－Ｓ－トリアジン、２－（ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン、２－（４－エトキシ－ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン、２－（４－ブトキシ－ナフト－１－イル）－４，６－ビス－トリクロロメチル－Ｓ－トリアジン等のハロメチル－Ｓ－トリアジン系化合物、２，２－ジメトキシ－１，２－ジフェニルエタン－１－オン、２－メチル－１－〔４－（メチルチオ）フェニル〕－２－モルフォリノプロパノン、１，２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）－ブタノン－１，１－ヒドロキシ－シクロヘキシル－フェニルケトン、ベンジル、ベンゾイル安息香酸、ベンゾイル安息香酸メチル、４－ベンゾイル－４’－メチルジフェニルサルファイド、ベンジルメチルケタール、ジメチルアミノベンゾエート、ｐ－ジメチルアミノ安息香酸イソアミル、２－ｎ－ブトキシエチル－４－ジメチルアミノベンゾエート、２－クロロチオキサントン、２，４－ジエチルチオキサントン、２，４－ジメチルチオキサントン、イソプロピルチオキサントン、１－（４－フェニルチオフェニル）－１，２－オクタンジオン－２－（Ｏ－ベンゾイルオキシム）、エタノン，１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、４－ベンゾイル－メチルジフェニルサルファイド、１－ヒドロキシ－シクロヘキシル－フェニルケトン、２－ベンジル－２－（ジメチルアミノ）－１－［４－（４－モルフォリニル）フェニル］－１－ブタノン、２－（ジメチルアミノ）－２－［（４－メチルフェニル）メチル］－１－［４－（４－モルホリニル）フェニル］－１－ブタノン、α－ジメトキシ－α－フェニルアセトフェノン、フェニルビス（２，４，６－トリメチルベンゾイル）フォスフィンオキサイド、ジフェニル（２，４，６－トリメチルベンゾイル）フォスフィンオキサイド、２－メチル－１－［４－（メチルチオ）フェニル］－２－（４－モルフォリニル）－１－プロパノン等が挙げられる。
　上記の光ラジカル発生剤は、市販品として容易に入手が可能であり、その具体例としては、例えばＩＲＧＡＣＵＲＥ１７３、ＩＲＧＡＣＵＲＥ　５００、ＩＲＧＡＣＵＲＥ　２９５９、ＩＲＧＡＣＵＲＥ　７５４、ＩＲＧＡＣＵＲＥ　９０７、ＩＲＧＡＣＵＲＥ　３６９、ＩＲＧＡＣＵＲＥ　１３００、ＩＲＧＡＣＵＲＥ　８１９、ＩＲＧＡＣＵＲＥ　８１９ＤＷ、ＩＲＧＡＣＵＲＥ　１８８０、ＩＲＧＡＣＵＲＥ　１８７０、ＤＡＲＯＣＵＲＥ　ＴＰＯ、ＤＡＲＯＣＵＲＥ　４２６５、ＩＲＧＡＣＵＲＥ　７８４、ＩＲＧＡＣＵＲＥ　ＯＸＥ０１、ＩＲＧＡＣＵＲＥ　ＯＸＥ０２、ＩＲＧＡＣＵＲＥ　ＯＸＥ０３、ＩＲＧＡＣＵＲＥ　ＯＸＥ０４、ＩＲＧＡＣＵＲＥ　２５０（以上、ＢＡＳＦ社製）、ＫＡＹＡＣＵＲＥ　ＤＥＴＸ－Ｓ、ＫＡＹＡＣＵＲＥ　ＣＴＸ、ＫＡＹＡＣＵＲＥ　ＢＭＳ、ＫＡＹＡＣＵＲＥ　２－ＥＡＱ（以上、日本化薬（株）製）、ＴＡＺ－１０１、ＴＡＺ－１０２、ＴＡＺ－１０３、ＴＡＺ－１０４、ＴＡＺ－１０６、ＴＡＺ－１０７、ＴＡＺ－１０８、ＴＡＺ－１１０、ＴＡＺ－１１３、ＴＡＺ－１１４、ＴＡＺ－１１８、ＴＡＺ－１２２、ＴＡＺ－１２３、ＴＡＺ－１４０、ＴＡＺ－２０４（以上みどり化学（株）製）等が挙げられる。
　これらの光ラジカル発生剤単独で使用しても、二種類以上を併用することも可能である。 (D-2) The photoradical generator is not particularly limited as long as it generates radicals by exposure. Specific examples include the same components as (D-2) mentioned in the component (D) used in the above-mentioned composition for forming an upper layer film.
Specific examples include aromatic ketones such as benzophenone, Michler ketone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene, benzoin methyl ether, and benzoin ethyl. Benzoin ethers such as ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5- Di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-Triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4) -Mophorinophenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazol, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole , 2-Trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and other halomethyloxaziazole compounds, 2,4-bis (trichloromethyl) -6-p-methoxystyryl- S-Triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxy Styryl-S-triazine, 2- (naphth-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis-trichloro Halomethyl-S-triazine compounds such as methyl-S-triazine, 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-Diphenylethane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanol, 1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl -4'-Methyldiphenylsulfide, benzylmethylketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2 , 4-Dimethylthioxanthone, Isopropylthioxanthone, 1- (4-Phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime), Etanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1 -[4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl-1- [4 -(Methylthio) phenyl] -2- (4-morpholinyl) -1-propanone and the like.
The above photoradical generator is easily available as a commercially available product, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, and IRGACURE 819. 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE03, IRGACURE OXE03, IRGACURE OXE04, IRGACURE04, IRGACURE04 KAYACURE 2-EAQ (all manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ- 113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.) and the like can be mentioned.
It is possible to use these photoradical generators alone or to use two or more of them in combination.
　本発明の感光性樹脂組成物に（Ｄ－２）成分を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して０．１質量部乃至３０質量部であることが好ましく、より好ましくは０．５質量部乃至２０質量部であり、特に好ましくは１質量部乃至１５質量部である。この割合が過小である場合には、露光部が硬化不足となり、パターン形成ができなかったり、できたとしても信頼性の低い膜となる場合がある。また、この割合が過大である場合には、塗膜の透過率が低下したり、未露光部の現像不良が起こったりする場合がある。 When the photosensitive resin composition of the present invention contains the component (D-2), the content thereof is 0.1 part by mass to 30 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B). It is preferably 0.5 parts by mass to 20 parts by mass, and particularly preferably 1 part by mass to 15 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, the transmittance of the coating film may decrease or development failure of the unexposed portion may occur.
　（Ｄ－３）の光酸発生剤は紫外線照射時に光分解して酸を発生する化合物であれば特に限定されるものではない。光酸発生剤が光分解した際に発生する酸としては、例えば、塩酸、メタンスルホン酸、エタンスルホン酸、プロパンスルホン酸、ブタンスルホン酸、ペンタンスルホン酸、オクタンスルホン酸、ベンゼンスルホン酸、ｐ－トルエンスルホン酸、カンファスルホン酸、トリフルオロメタンスルホン酸、ｐ－フェノールスルホン酸、２－ナフタレンスルホン酸、メシチレンスルホン酸、ｐ－キシレン－２－スルホン酸、ｍ－キシレン－２－スルホン酸、４－エチルベンゼンスルホン酸、１Ｈ，１Ｈ，２Ｈ，２Ｈ－パーフルオロオクタンスルホン酸、パーフルオロ（２－エトキシエタン）スルホン酸、ペンタフルオロエタンスルホン酸、ノナフルオロブタン－１－スルホン酸、ドデシルベンゼンスルホン酸等のスルホン酸又はその水和物や塩等が挙げられる。 The photoacid generator of (D-3) is not particularly limited as long as it is a compound that photodecomposes to generate an acid when irradiated with ultraviolet rays. Examples of the acid generated when the photoacid generator is photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-. Toluene sulfonic acid, campha sulfonic acid, trifluoromethane sulfonic acid, p-phenol sulfonic acid, 2-naphthalene sulfonic acid, mesitylen sulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H, 1H, 2H, 2H-perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid and other sulfonic acids Examples thereof include acid or its hydrate and salt.
　光酸発生剤としては、例えば、ジアゾメタン化合物、オニウム塩化合物、スルホンイミド化合物、ジスルホン系化合物、スルホン酸誘導体化合物、ニトロベンジル化合物、ベンゾイントシレート化合物、鉄アレーン錯体、ハロゲン含有トリアジン化合物、アセトフェノン誘導体化合物、及び、シアノ基含有オキシムスルホネート化合物などが挙げられる。従来知られ又は従来から使用されている光酸発生剤は、いずれも、特に限定されることなく、本発明において適用することができる。なお、本発明において、（Ｄ）成分の光酸発生剤は、一種単独で用いてもよく、また二種以上を組み合わせて用いてもよい。具体例としては、下記式［ＰＡＧ－１］～式［ＰＡＧ－４１］で表される化合物等を挙げることができる。 Examples of the photoacid generator include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. , And a cyano group-containing oxime sulfonate compound and the like. Any of the conventionally known or conventionally used photoacid generators can be applied in the present invention without particular limitation. In the present invention, the photoacid generator of the component (D) may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　本実施の形態の感光性樹脂組成物に（Ｄ－３）成分を含有させる場合の含有量は、（Ａ）成分と（Ｂ）成分の合計１００質量部に対して、好ましくは０．０１質量部乃至２０質量部、より好ましくは０．１質量部乃至１０質量部、更に好ましくは０．５質量部乃至８質量部である。（Ｄ－３）成分の含有量を０．０１質量部以上とすることで、充分な熱硬化性および溶剤耐性を付与することができる。しかし、２０質量部より多い場合、未露光部が現像不良となったり、組成物の保存安定性が低下する場合がある。 When the photosensitive resin composition of the present embodiment contains the component (D-3), the content thereof is preferably 0.01 mass by mass with respect to 100 parts by mass of the total of the components (A) and (B). Parts to 20 parts by mass, more preferably 0.1 parts to 10 parts by mass, still more preferably 0.5 parts to 8 parts by mass. By setting the content of the component (D-3) to 0.01 parts by mass or more, sufficient thermosetting property and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, the unexposed part may be poorly developed or the storage stability of the composition may be lowered.
＜（Ｅ）成分＞
　（Ｅ）成分は架橋剤であり、本発明の感光性樹脂組成物が要件（Ｚ１）を満たす場合に組成物中に導入されるものである。より具体的には、（Ａ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性ヒドロキシ基）と熱反応により橋架け構造を形成しうる構造を有する化合物である。以下、具体例を挙げるがこれらに限定されるものではない。熱架橋剤は、例えば、（Ｅ１）アルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物や（Ｅ２）下記式（２）で表される架橋性化合物から選ばれるものが好ましい。これらの架橋剤は単独または２種以上の組み合わせで使用することができる。 <Ingredient (E)>
The component (E) is a cross-linking agent, which is introduced into the composition when the photosensitive resin composition of the present invention satisfies the requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridging structure by a thermal reaction with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A). Specific examples will be given below, but the present invention is not limited to these. The thermal cross-linking agent is selected from, for example, a cross-linking compound having two or more substituents selected from (E1) alkoxymethyl group and hydroxymethyl group, and (E2) cross-linking compound represented by the following formula (2). Is preferable. These cross-linking agents can be used alone or in combination of two or more.
　（Ｅ１）成分のアルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する架橋性化合物は、熱硬化時の高温に曝されると、脱水縮合反応により架橋反応が進行するものである。このような化合物としては、例えば、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、およびアルコキシメチル化メラミン等の化合物、およびフェノプラスト系化合物が挙げられる。 When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group of the component (E1) is exposed to a high temperature during heat curing, the crosslinking reaction proceeds by the dehydration condensation reaction. .. Examples of such compounds include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.
　アルコキシメチル化グリコールウリルの具体例としては、例えば、１，３，４，６－テトラキス（メトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ブトキシメチル）グリコールウリル、１，３，４，６－テトラキス（ヒドロキシメチル）グリコールウリル、１，３－ビス（ヒドロキシメチル）尿素、１，１，３，３－テトラキス（ブトキシメチル）尿素、１，１，３，３－テトラキス（メトキシメチル）尿素、１，３－ビス（ヒドロキシメチル）－４，５－ジヒドロキシ－２－イミダゾリノン、および１，３－ビス（メトキシメチル）－４，５－ジメトキシ－２－イミダゾリノン等が挙げられる。市販品として、三井サイテック（株）製グリコールウリル化合物（商品名：サイメル（登録商標）１１７０、パウダーリンク（登録商標）１１７４）等の化合物、メチル化尿素樹脂（商品名：ＵＦＲ（登録商標）６５）、ブチル化尿素樹脂（商品名：ＵＦＲ（登録商標）３００、Ｕ－ＶＡＮ１０Ｓ６０、Ｕ－ＶＡＮ１０Ｒ、Ｕ－ＶＡＮ１１ＨＶ）、ＤＩＣ（株）製尿素／ホルムアルデヒド系樹脂（高縮合型、商品名：ベッカミン（登録商標）Ｊ－３００Ｓ、同Ｐ－９５５、同Ｎ）等が挙げられる。 Specific examples of alkoxymethylated glycol uryl include 1,3,4,6-tetrax (methoxymethyl) glycol uryl, 1,3,4,6-tetrax (butoxymethyl) glycol uryl, 1,3,4. , 6-Tetrax (hydroxymethyl) glycoluryl, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) Examples thereof include urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone. As commercially available products, compounds such as glycoluril compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1170, powder link (registered trademark) 1174), methylated urea resin (trade name: UFR (registered trademark) 65) ), Butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea / formaldehyde resin manufactured by DIC Co., Ltd. (high condensation type, trade name: Beccamin () Registered trademarks) J-300S, P-955, N) and the like.
　アルコキシメチル化ベンゾグアナミンの具体例としてはテトラメトキシメチルベンゾグアナミン等が挙げられる。市販品として、三井サイテック（株）製（商品名：サイメル（登録商標）１１２３）、（株）三和ケミカル製（商品名：ニカラック（登録商標）ＢＸ－４０００、同ＢＸ－３７、同ＢＬ－６０、同ＢＸ－５５Ｈ）等が挙げられる。 Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. As commercial products, Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (trade name: Nicarac (registered trademark) BX-4000, BX-37, BL- 60, BX-55H) and the like.
　アルコキシメチル化メラミンの具体例としては、例えば、ヘキサメトキシメチルメラミン等が挙げられる。市販品として、三井サイテック（株）製メトキシメチルタイプメラミン化合物（商品名：サイメル（登録商標）３００、同３０１、同３０３、同３５０）、ブトキシメチルタイプメラミン化合物（商品名：マイコート（登録商標）５０６、同５０８）、三和ケミカル製メトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＷ－３０、同ＭＷ－２２、同ＭＷ－１１、同ＭＷ－１００ＬＭ、同ＭＳ－００１、同ＭＸ－００２、同ＭＸ－７３０、同ＭＸ－７５０、同ＭＸ－０３５）、ブトキシメチルタイプメラミン化合物（商品名：ニカラック（登録商標）ＭＸ－４５、同ＭＸ－４１０、同ＭＸ－３０２）等が挙げられる。 Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 300, 301, 303, 350), butoxymethyl type melamine compound (trade name: Mycoat (registered trademark)). ) 506, 508), Sanwa Chemical's methoxymethyl type melamine compound (trade name: Nicarac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MS-001, same MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nicarac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３（三井サイテック（株）製）等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（三井サイテック（株）製）等が挙げられる。 Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.
　フェノプラスト系化合物の具体例としては、例えば、２，６－ビス（ヒドロキシメチル）フェノール、２，６－ビス（ヒドロキシメチル）クレゾール、２，６－ビス（ヒドロキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（ヒドロキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－ヒドロキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－ヒドロキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（ヒドロキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（ヒドロキシメチル）フェノール］、２，６－ビス（メトキシメチル）フェノール、２，６－ビス（メトキシメチル）クレゾール、２，６－ビス（メトキシメチル）－４－メトキシフェノール、３，３’，５，５’－テトラキス（メトキシメチル）ビフェニル－４，４’－ジオール、３，３’－メチレンビス（２－メトキシ－５－メチルベンゼンメタノール）、４，４’－（１－メチルエチリデン）ビス［２－メチル－６－メトキシメチルフェノール］、４，４’－メチレンビス［２－メチル－６－メトキシメチルフェノール］、４，４’－（１－メチルエチリデン）ビス［２，６－ビス（メトキシメチル）フェノール］、４，４’－メチレンビス［２，６－ビス（メトキシメチル）フェノール］、等が挙げられる。市販品としても入手が可能であり、その具体例としては、２６ＤＭＰＣ、４６ＤＭＯＣ、ＤＭ－ＢＩＰＣ－Ｆ、ＤＭ－ＢＩＯＣ－Ｆ、ＴＭ－ＢＩＰ－Ａ、ＢＩＳＡ－Ｆ、ＢＩ２５Ｘ－ＤＦ、ＢＩ２５Ｘ－ＴＰＡ（以上、旭有機材工業（株）製）等が挙げられる。 Specific examples of the phenoplast compound include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, 2,6-bis (hydroxymethyl) -4-methoxyphenol, and 3 , 3', 5,5'-tetrax (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl) Ethiliden) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene) bis [2,6- Bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2,6-bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2 , 6-bis (methoxymethyl) -4-methoxyphenol, 3,3', 5,5'-tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-methoxy-5) -Methylbenzene methanol), 4,4'-(1-methylethylidene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxymethylphenol], 4, Examples thereof include 4'-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) phenol], and the like. It is also available as a commercially available product, and specific examples thereof include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( As mentioned above, Asahi Organic Materials Industry Co., Ltd.) and the like can be mentioned.
　さらに、（Ｅ１）成分としては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のヒドロキシメチル基またはアルコキシメチル基で置換されたアクリルアミド化合物またはメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。 Further, as the component (E1), an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.
　そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、１，０００乃至５０，０００であり、好ましくは、１，５００乃至２０，０００であり、より好ましくは２，０００乃至１０，０００である。 Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.
　また本発明の感光性樹脂組成物は、（Ｅ２）成分として、下記式（２）で表される架橋性化合物を含有することができる。
Figure JPOXMLDOC01-appb-C000019
 （式中、ｋは２乃至１０の整数、ｍは０乃至４の整数を示し、Ｒはｋ価の有機基を表す） Further, the photosensitive resin composition of the present invention can contain a crosslinkable compound represented by the following formula (2) as the component (E2).
Figure JPOXMLDOC01-appb-C000019
 (In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R represents a k-valent organic group.)
　（Ｅ２）成分は、式（２）で表されるシクロアルケンオキサイド構造を有する化合物であれば特に限定されない。その具体例としては、下記式Ｅ２－１及び式Ｅ２－２や、以下に示す市販品等が挙げられる。
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
 The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by the formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, and commercially available products shown below.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000021
　市販品としては、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（ダイセル（株）製　商品名）、脂環式エポキシ樹脂であるデナコールＥＸ－２５２（ナガセケムテックス（株）製　商品名）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９（以上、Ｈｕｎｔｓｍａｎ　Ｃｏｒｐｏｒａｔｉｏｎ製　商品名）、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、Ｈｕｎｔｓｍａｎ　Ｃｏｒｐｏｒａｔｉｏｎ製　商品名）、エピクロン２００、同４００（以上、ＤＩＣ（株）製　商品名）、エピコート８７１、同８７２（以上、三菱ケミカル（株）製　商品名）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製　商品名）、等を挙げることができる。また、これらの架橋性化合物は、単独または２種類以上を組み合わせて用いることができる。 Commercially available products include Epolide GT-401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (trade name manufactured by Daicel Co., Ltd.), and Denacol EX-, which is an alicyclic epoxy resin. 252 (Product name of Nagase ChemteX Corporation), CY175, CY177, CY179 (Product name of Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (Product name of Huntsman Corporation) ), Epicron 200, 400 (above, DIC Co., Ltd. product name), Epicoat 871, 872 (above, Mitsubishi Chemical Co., Ltd. product name), ED-5661, ED-5662 (above, Ceranies Coating) Product name manufactured by Huntsman Corporation), etc. can be mentioned. In addition, these crosslinkable compounds can be used alone or in combination of two or more.
　これらのうち、耐熱性、耐溶剤性、耐長時間焼成耐性等の耐プロセス性、および透明性の観点からシクロヘキセンオキサイド構造を有する、式Ｅ２－１及び式Ｅ２－２で表される化合物、エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００が好ましい。 Among these, the compounds represented by the formulas E2-1 and E2-2, which have a cyclohexene oxide structure from the viewpoint of process resistance such as heat resistance, solvent resistance, long-term firing resistance, and transparency, epolide. GT-401, GT-403, GT-301, GT-302, sinterside 2021, and seroxside 3000 are preferable.
　また、Ｅ成分としては（Ｅ１）成分、（Ｅ２）成分として示したもの以外の（Ａ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性ヒドロキシ基）と熱反応により橋架け構造を形成しうる化合物も用いることができる。具体的には、例えば、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリンジグリシジルエーテル、２，２－ジブロモネオペンチルグリコールジグリシジルエーテル、１，３，５，６－テトラグリシジル－２，４－ヘキサンジオール、Ｎ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－ｍ－キシレンジアミン、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン、及びＮ，Ｎ，Ｎ’，Ｎ’，－テトラグリシジル－４、４’－ジアミノジフェニルメタン等のエポキシ化合物、ＶＥＳＴＡＮＡＴ　Ｂ１３５８／１００、ＶＥＳＴＡＧＯＮ　ＢＦ　１５４０（以上、イソシアヌレート型変性ポリイソシアネート、デグサジャパン（株）製）、タケネート（登録商標）Ｂ－８８２Ｎ、同タケネートＢ―７０７５（以上、イソシアヌレート型変性ポリイソシアネート、三井化学（株）製）等のイソシアネート化合物等が挙げられる。 Further, the E component is a structure bridged by a thermal reaction with a heat-reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A) other than those shown as the component (E1) and the component (E2). Compounds that can form the above can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane. Didiol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N', N', -Tetraglycidyl-m-isocyanateamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, and N, N, N', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, etc. Epoxy compound, VESTANAT B1358 / 100, VESTAGON BF 1540 (above, isocyanurate-type modified polyisocyanate, manufactured by Degusa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (above, isocyanurate-type modified) Examples thereof include polyisocyanates and isocyanate compounds manufactured by Mitsui Kagaku Co., Ltd.
　また、Ｅ成分としては（Ａ）成分の熱反応性部位（たとえば、カルボキシル基及び／又はフェノール性ヒドロキシ基）と熱反応により橋架け構造を形成しうる構造を２個以上有する重合体を用いることができる。具体的には、例えば、グリシジルメタクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート、３，４－エポキシシクロヘキシルメチルメタクリレート等のエポキシ基を有する化合物を使用して製造されるポリマー、３－メタクリロキシプロピルトリメトキシシラン等のアルコキシシリル基を有する化合物を使用して製造されるポリマー、２－イソシアナトエチルメタクリレート（カレンズＭＯＩ［登録商標］、昭和電工（株）製）、２－イソシアナトエチルアクリレート（カレンズＡＯＩ［登録商標］、昭和電工（株）製）等のイソシアナート基を有する化合物、または２－（０－［１’－メチルプロピリデンアミノ］カルボキシアミノ）エチルメタクリレート（カレンズＭＯＩ－ＢＭ［登録商標］、昭和電工（株）製）、２－［（３，５－ジメチルピラゾリル）カルボニルアミノ］エチルメタクリレート（カレンズＭＯＩ－ＢＰ［登録商標］、昭和電工（株）製）等のブロックイソシアネート基を有する化合物を使用して製造されるポリマーが挙げられる。これらの化合物は単独、もしくは複数を組み合わせて使用してポリマーを製造しても良く、そのほかの化合物と組み合わせてポリマーを製造しても良い。 Further, as the E component, a polymer having two or more structures capable of forming a bridging structure by a thermal reaction with the heat-reactive site (for example, a carboxyl group and / or a phenolic hydroxy group) of the component (A) is used. Can be done. Specifically, 3-methacryloxypropyltrimethoxy, a polymer produced using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxide cyclohexylmethyl methacrylate, or 3,4-epoxide cyclohexylmethyl methacrylate. Polymers produced using compounds having an alkoxysilyl group such as silane, 2-isocyanatoethyl methacrylate (Kalens MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Kalens AOI [ Registered trademark], compounds having an isocyanate group such as Showa Denko Co., Ltd., or 2- (0- [1'-methylpropyrideneamino] carboxyamino) ethyl methacrylate (Karens MOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Karenzu MOI-BP [registered trademark], Showa Denko Co., Ltd.) and other compounds with a blocked isocyanate group. Examples include polymers produced using. These compounds may be used alone or in combination of two or more to produce a polymer, or may be combined with other compounds to produce a polymer.
　（Ａ）成分がヒドロキシ基、カルボキシル基、アミド基、アミノ基で表される基からなる群から選択される少なくとも１つの基と反応する基を有する場合には、ヒドロキシ基、カルボキシル基、アミド基、アミノ基で表される基を２つ以上有する化合物を（Ｅ）成分として用いることができる。 When the component (A) has a group that reacts with at least one group selected from the group consisting of a group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group, the hydroxy group, the carboxyl group and the amide group , A compound having two or more groups represented by amino groups can be used as the component (E).
　これらの架橋性化合物は、単独でまたは２種以上を組み合わせて使用することができる。 These crosslinkable compounds can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物における架橋剤として（Ｅ）成分を選択した場合の含有量は、（Ａ）成分の１００質量部に対して１質量部乃至５０質量部、好ましくは１質量部乃至４０質量部、より好ましくは１質量部乃至３０質量部である。架橋性化合物の含有量が少ない場合には、架橋性化合物によって形成される架橋の密度が十分ではないため、パターン形成後の耐熱性、耐溶剤性、長時間の焼成に対する耐性等を向上させる効果が得られない場合がある。一方、５０質量部を超える場合には、未架橋の架橋性化合物が存在し、パターン形成後の耐熱性、耐溶剤性、長時間の焼成に対する耐性等が低下し、また、感光性樹脂組成物の保存安定性が悪くなる場合がある。 When the component (E) is selected as the cross-linking agent in the photosensitive resin composition of the present invention, the content is 1 part by mass to 50 parts by mass, preferably 1 part by mass or more with respect to 100 parts by mass of the component (A). It is 40 parts by mass, more preferably 1 part to 30 parts by mass. When the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so that the effect of improving the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation is improved. May not be obtained. On the other hand, when it exceeds 50 parts by mass, an uncrosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are lowered, and the photosensitive resin composition Storage stability may deteriorate.
＜（Ｆ）成分＞
　（Ｆ）成分はエチレン性重合性基を２個以上有する化合物である。ここで言うところのエチレン性重合性基を２個以上有する化合物とは、一分子中に重合性基を２個以上有し、且つそれらの重合性基が分子末端にある化合物のことを意味し、それらの重合性基とは、アクリレート基、メタクリレート基、ビニル基及びアリル基からなる群から選択される少なくとも１種類の重合性基のことを意味する。
　この（Ｆ）成分であるエチレン性重合性基を２個以上有する化合物は、本発明の感光性樹脂組成物におけるネガ型感光性樹脂組成物の溶液において、各成分との相溶性が良好で、且つ現像性に影響を与えないという観点から、分子量（該化合物がポリマーである場合、重量平均分子量）が１，０００以下の化合物が好ましい。 <(F) component>
The component (F) is a compound having two or more ethylenically polymerizable groups. The term "compound having two or more ethylenically polymerizable groups" as used herein means a compound having two or more polymerizable groups in one molecule and having those polymerizable groups at the molecular ends. , Those polymerizable groups mean at least one kind of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group and an allyl group.
The compound having two or more ethylenically polymerizable groups as the component (F) has good compatibility with each component in the solution of the negative type photosensitive resin composition in the photosensitive resin composition of the present invention. Moreover, from the viewpoint of not affecting the developability, a compound having a molecular weight (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.
　このような化合物の具体例としては、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ペンタエリスリトールテトラアクリレート、ペンタエリスリトールテトラメタクリレート、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、ペンタエリスリトールジアクリレート、ペンタエリスリトールジメタクリレート、テトラメチロールプロパンテトラアクリレート、テトラメチロールプロパンテトラメタクリレート、テトラメチロールメタンテトラアクリレート、テトラメチロールメタンテトラメタクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、１，３，５－トリアクリロイルヘキサヒドロ－Ｓ－トリアジン、１，３，５－トリメタクリロイルヘキサヒドロ－Ｓ－トリアジン、トリス（ヒドロキシエチルアクリロイル）イソシアヌレート、トリス（ヒドロキシエチルメタクリロイル）イソシアヌレート、トリアクリロイルホルマール、トリメタクリロイルホルマール、１，６－ヘキサンジオールアクリレート、１，６－ヘキサンジオールメタクリレート、ネオペンチルグリコールジアクリレート、ネオペンチルグリコールジメタクリレート、エタンジオールジアクリレート、エタンジオールジメタクリレート、２－ヒドロキシプロパンジオールジアクリレート、２－ヒドロキシプロパンジオールジメタクリレート、ジエチレングリコールジアクリレート、ジエチレングリコールジメタクリレート、イソプロピレングリコールジアクリレート、イソプロピレングリコールジメタクリレート、トリエチレングリコールジアクリレート、トリエチレングリコールジメタクリレート、Ｎ，Ｎ’－ビス（アクリロイル）システイン、Ｎ，Ｎ’－ビス（メタクリロイル）システイン、チオジグリコールジアクリレート、チオジグリコールジメタクリレート、ビスフェノールＡジアクリレート、ビスフェノールＡジメタクリレート、ビスフェノールＦジアクリレート、ビスフェノールＦジメタクリレート、ビスフェノールＳジアクリレート、ビスフェノールＳジメタクリレート、ビスフェノキシエタノールフルオレンジアクリレート、ビスフェノキシエタノールフルオレンジメタクリレート、ジアリルエーテルビスフェノールＡ、ｏ―ジアリルビスフェノールＡ、マレイン酸ジアリル、トリアリルトリメリテート等が挙げられる。 Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and penta. Elythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropanetetraacrylate, tetramethylolpropanetetramethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, 1,3,5-triacryloyl hexahydro-S-triazine, 1,3,5-trimethacryloyl hexahydro-S-triazine, tris (hydroxyethylacryloyl) isocyanurate, tris (hydroxyethylmethacryloyl) isocyanurate, triacryloyl Formal, Trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol di Acrylate, 2-Hydroxypropanediol dimethacrylate, Diethylene glycol diacrylate, Diethylene glycol dimethacrylate, Isopropylene glycol diacrylate, Isopropylene glycol dimethacrylate, Triethylene glycol diacrylate, Triethylene glycol dimethacrylate, N, N'-bis (acryloyl) ) Cysteine, N, N'-bis (methacryloyl) cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate , Bisphenol S dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, diallylate Examples thereof include terbisphenol A, o-diallyl bisphenol A, diallyl maleate, and triallyl trimellitate.
　上記の多官能アクリレート化合物は、市販品として容易に入手が可能であり、その具体例としては、例えばＫＹＡＲＡＤ　Ｔ－１４２０、同ＤＰＨＡ、同ＤＰＨＡ－２Ｃ、同Ｄ－３１０、同Ｄ－３３０、同ＤＰＣＡ－２０、同ＤＰＣＡ－３０、同ＤＰＣＡ－６０、同ＤＰＣＡ－１２０、同ＤＮ－００７５、同ＤＮ－２４７５、同Ｒ－５２６、同ＮＰＧＤＡ、同ＰＥＧ４００ＤＡ、同ＭＡＮＤＡ、同Ｒ－１６７、同ＨＸ－２２０、同ＨＸ６２０、同Ｒ－５５１、同Ｒ－７１２、同Ｒ－６０４、同Ｒ－６８４、同ＧＰＯ－３０３、同ＴＭＰＴＡ、同ＴＨＥ－３３０、同ＴＰＡ－３２０、同ＴＰＡ－３３０、同ＰＥＴ－３０、同ＲＰ－１０４０（以上、日本化薬（株）製）、アロニックスＭ－２１０、同Ｍ－２４０、同Ｍ－６２００、同Ｍ－３０９、同Ｍ－４００、同Ｍ－４０２、同Ｍ－４０５、同Ｍ－４５０、同Ｍ－７１００、同Ｍ－８０３０、同Ｍ－８０６０、同Ｍ－１３１０、同Ｍ－１６００、同Ｍ－１９６０、同Ｍ－８１００、同Ｍ－８５３０、同Ｍ－８５６０、同Ｍ－９０５０（以上、東亞合成（株）製）、ビスコート２９５、同３００、同３６０、同ＧＰＴ、同３ＰＡ、同４００、同２６０、同３１２、同３３５ＨＰ（以上、大阪有機化学工業（株）製）、Ａ－９３００、Ａ－ＧＬＹ－９Ｅ、Ａ－ＧＬＹ－２０Ｅ、Ａ－ＴＭＭ－３、Ａ－ＴＭＭ－３Ｌ、Ａ－ＴＭＭ－３ＬＭ－Ｎ、Ａ－ＴＭＰＴ、ＡＤ－ＴＭＰ、ＡＴＭ－３５Ｅ、Ａ－ＴＭＭＴ、Ａ－９５５０、Ａ－ＤＰＨ、ＴＭＰＴ、９ＰＧ、７０１、１２０６ＰＥ、ＮＰＧ、ＮＯＤ－Ｎ，ＨＤ－Ｎ，ＤＯＤ－Ｎ，ＤＣＰ，ＢＰＥ－１３００Ｎ，ＢＰＥ－９００，ＢＰＥ－２００，ＢＰＥ－１００，ＢＰＥ－８０Ｎ，２３Ｇ，１４Ｇ，９Ｇ，４Ｇ，３Ｇ，２Ｇ，１Ｇ　（以上、新中村化学工業（株）製）等を挙げることができる。
　これらのエチレン性重合性基を２個以上有する化合物は１種または２種以上を組み合わせて用いることができる。 The above-mentioned polyfunctional acrylate compound can be easily obtained as a commercially available product, and specific examples thereof include, for example, KYARAD T-1420, DPHA, DPHA-2C, D-310, D-330, and D-330. DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (above, manufactured by Toa Synthetic Co., Ltd.), Viscort 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (above, Osaka) Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD -TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900 , BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.) and the like.
The compounds having two or more of these ethylenically polymerizable groups can be used alone or in combination of two or more.
　本発明の感光性樹脂組成物に（Ｆ）成分を含有させる場合の含有量は、（Ａ）成分１００質量部に対して５質量部乃至２００質量部であることが好ましく、より好ましくは１０質量部乃至１５０質量部であり、特に好ましくは５０質量部乃至１５０質量部である。この割合が過小である場合には、露光部が硬化不足となり、パターン形成ができなかったり、できたとしても信頼性の低い膜となる可能性がある。また、この割合が過大である場合には、プリベーク後の塗膜にタックが発生したり、現像時に未露光部が溶解不良となる場合がある。 When the photosensitive resin composition of the present invention contains the component (F), the content is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass with respect to 100 parts by mass of the component (A). It is 10 parts to 150 parts by mass, and particularly preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the exposed portion may be insufficiently cured, and pattern formation may not be possible, or even if it is possible, the film may have low reliability. On the other hand, if this ratio is excessive, tack may occur in the coating film after prebaking, or the unexposed portion may be poorly dissolved during development.
＜（Ｇ）成分＞
　本発明の感光性樹脂組成物に用いられる（Ｇ）成分は、酸により共有結合を形成する官能基を２個以上有する化合物である。このような酸により共有結合を形成する官能基としてはエポキシ基、アルコキシメチル基、ヒドロキシメチル基等が挙げられる。 <(G) component>
The component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid. Examples of the functional group that forms a covalent bond with such an acid include an epoxy group, an alkoxymethyl group, and a hydroxymethyl group.
　エポキシ基を２個以上有する化合物としては、例えば、トリス（２，３－エポキシプロピル）イソシアヌレート、１，４－ブタンジオールジグリシジルエーテル、１，２－エポキシ－４－（エポキシエチル）シクロヘキサン、グリセロールトリグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、２，６－ジグリシジルフェニルグリシジルエーテル、１，１，３－トリス［ｐ－（２，３－エポキシプロポキシ）フェニル］プロパン、１，２－シクロヘキサンジカルボン酸ジグリシジルエステル、４，４’－メチレンビス（Ｎ，Ｎ－ジグリシジルアニリン）、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、トリメチロールエタントリグリシジルエーテル及びビスフェノール－Ａ－ジグリシジルエーテル、及びペンタエリスリトールポリグリシジルエーテル等を挙げることができる。 Examples of the compound having two or more epoxy groups include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4- (epoxyethyl) cyclohexane, and glycerol. Triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris [p- (2,3-epoxypropoxy) phenyl] propane, diglycidyl 1,2-cyclohexanedicarboxylate Esters, 4,4'-methylenebis (N, N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethanetriglycidyl ether and bisphenol-A-diglycidyl ether, And pentaerythritol polyglycidyl ether and the like.
　また、エポキシ基を２個以上有する化合物としては、入手が容易である点から市販品の化合物を用いてもよい。以下にその具体例（商品名）を挙げるが、これらに限定されるものではない：ＹＨ－４３４、ＹＨ４３４Ｌ（新日化エポキシ製造（株）製）等のアミノ基を有するエポキシ樹脂；エポリードＧＴ－４０１、同ＧＴ－４０３、同ＧＴ－３０１、同ＧＴ－３０２、セロキサイド２０２１、セロキサイド３０００（ダイセル（株）製）等のシクロヘキセンオキサイド構造を有するエポキシ樹脂；エピコート１００１、同１００２、同１００３、同１００４、同１００７、同１００９、同１０１０、同８２８（以上、油化シェルエポキシ（株）（現三菱ケミカル（株））製）等のビスフェノールＡ型エポキシ樹脂；エピコート８０７（油化シェルエポキシ（株）（現三菱ケミカル（株））製）等のビスフェノールＦ型エポキシ樹脂；エピコート１５２、同１５４（以上、油化シェルエポキシ（株）（現三菱ケミカル（株））製）、ＥＰＰＮ２０１、同２０２（以上、日本化薬（株）製）等のフェノールノボラック型エポキシ樹脂；ＥＯＣＮ－１０２、ＥＯＣＮ－１０３Ｓ、ＥＯＣＮ－１０４Ｓ、ＥＯＣＮ－１０２０、ＥＯＣＮ－１０２５、ＥＯＣＮ－１０２７（以上、日本化薬（株）製）、エピコート１８０Ｓ７５（油化シェルエポキシ（株）（現三菱ケミカル（株））製）等のクレゾールノボラック型エポキシ樹脂；デナコールＥＸ－２５２（ナガセケムテックス（株）製）、ＣＹ１７５、ＣＹ１７７、ＣＹ１７９、アラルダイトＣＹ－１８２、同ＣＹ－１９２、同ＣＹ－１８４（以上、Ｈｕｎｔｓｍａｎ　Ｃｏｒｐｏｒａｔｉｏｎ製）、エピクロン２００、同４００（以上、大日本インキ化学工業（株）（現ＤＩＣ（株））製）、エピコート８７１、同８７２（以上、油化シェルエポキシ（株）（現三菱ケミカル（株））製）、ＥＤ－５６６１、ＥＤ－５６６２（以上、セラニーズコーティング（株）製）等の脂環式エポキシ樹脂；デナコールＥＸ－６１１、同ＥＸ－６１２、同ＥＸ－６１４、同ＥＸ－６２２、同ＥＸ－４１１、同ＥＸ－５１２、同ＥＸ－５２２、同ＥＸ－４２１、同ＥＸ－３１３、同ＥＸ－３１４、同ＥＸ－３２１（ナガセケムテックス（株）製）等の脂肪族ポリグリシジルエーテル等。 Further, as the compound having two or more epoxy groups, a commercially available compound may be used because it is easily available. Specific examples (trade names) thereof are given below, but the present invention is not limited to these: epoxy resins having an amino group such as YH-434 and YH434L (manufactured by Shin Nikka Epoxy Manufacturing Co., Ltd.); Epoxy GT- Epoxy resins having a cyclohexene oxide structure such as 401, GT-403, GT-301, GT-302, seroxide 2021, seroxide 3000 (manufactured by Daicel Co., Ltd.); Epicoat 1001, 1002, 1003, 1004 , 1007, 1009, 1010, 828 (above, oiled shell epoxy Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.)) and other bisphenol A type epoxy resins; Epicoat 807 (oiled shell epoxy Co., Ltd.) Bisphenol F type epoxy resin (currently manufactured by Mitsubishi Chemical Co., Ltd.), etc .; Epicoat 152, 154 (currently manufactured by Yuka Shell Epoxy Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.)), EPPN201, 202 (currently manufactured) , Nippon Kayaku Co., Ltd.) and other phenol novolac type epoxy resins; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nihon Kayaku Co., Ltd.) ), Epicoat 180S75 (Oilized Shell Epoxy Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.)) and other cresol novolac type epoxy resins; Denacol EX-252 (manufactured by Nagase ChemteX Corporation), CY175, CY177, CY179, Araldite CY-182, CY-192, CY-184 (above, manufactured by Huntsman Corporation), Epoxy 200, 400 (above, manufactured by Dainippon Ink and Chemicals Co., Ltd. (currently DIC Co., Ltd.)), Epicoat 871 , 872 (above, oil-based shell epoxy Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.)), ED-5661, ED-5662 (above, manufactured by Ceranies Coating Co., Ltd.) and other alicyclic epoxy resins; Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, An aliphatic polyglycidyl ether such as EX-321 (manufactured by Nagase ChemteX Corporation).
　また、エポキシ基を２個以上有する化合物としてはエポキシ基を有するポリマーを使用することもできる。
　上記エポキシ基を有するポリマーは、例えばエポキシ基を有する付加重合性モノマーを用いた付加重合により製造することができる。一例として、ポリグリシジルアクリレート、グリシジルメタクリレートとエチルメタクリレートの共重合体、グリシジルメタクリレートとスチレンと２－ヒドロキシエチルメタクリレートの共重合体等の付加重合ポリマーや、エポキシノボラック等の縮重合ポリマーを挙げることができる。 Further, as the compound having two or more epoxy groups, a polymer having an epoxy group can also be used.
The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition-polymerizable monomer having an epoxy group. Examples thereof include addition polymerization polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and polycondensation polymers such as epoxy novolac. ..
　或いは、上記エポキシ基を有するポリマーは、ヒドロキシ基を有する高分子化合物とエピクロルヒドリン、グリシジルトシレート等のエポキシ基を有する化合物との反応により製造することもできる。 Alternatively, the polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin and glycidyltosilicate.
　このようなポリマーの重量平均分子量としては、例えば、３００乃至２０，０００である。 The weight average molecular weight of such a polymer is, for example, 300 to 20,000.
　これらのエポキシ基を２個以上有する化合物は、単独または２種以上の組み合わせで使用することができる。 Compounds having two or more of these epoxy groups can be used alone or in combination of two or more.
　アルコキシメチル基及びヒドロキシメチル基から選ばれる置換基を２個以上有する化合物は、例えば、アルコキシメチル化グリコールウリル、アルコキシメチル化ベンゾグアナミン、およびアルコキシメチル化メラミン等の化合物、およびフェノプラスト系化合物が挙げられる。 Examples of the compound having two or more substituents selected from the alkoxymethyl group and the hydroxymethyl group include compounds such as alkoxymethylated glycol uryl, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds. ..
　アルコキシメチル化グリコールウリルの具体例としては、上記の段落［０１００］で記載したとおりである。 Specific examples of alkoxymethylated glycol uryl are as described in the above paragraph [0100].
　アルコキシメチル化ベンゾグアナミンの具体例としては、上記の段落［０１０１］で記載したとおりである。 Specific examples of alkoxymethylated benzoguanamine are as described in the above paragraph [0101].
　アルコキシメチル化メラミンの具体例としては、上記の段落［０１０２］で記載したとおりである。 Specific examples of alkoxymethylated melamine are as described in the above paragraph [0102].
　また、このようなアミノ基の水素原子がメチロール基またはアルコキシメチル基で置換されたメラミン化合物、尿素化合物、グリコールウリル化合物及びベンゾグアナミン化合物を縮合させて得られる化合物であってもよい。例えば、米国特許第６３２３３１０号に記載されているメラミン化合物およびベンゾグアナミン化合物から製造される高分子量の化合物が挙げられる。前記メラミン化合物の市販品としては、商品名：サイメル（登録商標）３０３（三井サイテック（株）製）等が挙げられ、前記ベンゾグアナミン化合物の市販品としては、商品名：サイメル（登録商標）１１２３（三井サイテック（株）製）等が挙げられる。 Further, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. For example, high molecular weight compounds produced from the melamine and benzoguanamine compounds described in US Pat. No. 6,323,310. Examples of commercially available products of the melamine compound include trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the benzoguanamine compound include trade name: Cymel (registered trademark) 1123 ( Mitsui Cytec Co., Ltd.) and the like.
　フェノプラスト系化合物の具体例としては、上記の段落［０１０４］で記載したとおりである。 Specific examples of the phenoplast compound are as described in the above paragraph [0104].
　さらに、（Ｇ）成分としては、Ｎ－ヒドロキシメチルアクリルアミド、Ｎ－メトキシメチルメタクリルアミド、Ｎ－エトキシメチルアクリルアミド、Ｎ－ブトキシメチルメタクリルアミド等のヒドロキシメチル基またはアルコキシメチル基で置換されたアクリルアミド化合物またはメタクリルアミド化合物を使用して製造されるポリマーも用いることができる。 Further, as the component (G), an acrylamide compound substituted with a hydroxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or an alkoxymethyl group or Polymers made using methacrylamide compounds can also be used.
　そのようなポリマーとしては、例えば、ポリ（Ｎ－ブトキシメチルアクリルアミド）、Ｎ－ブトキシメチルアクリルアミドとスチレンとの共重合体、Ｎ－ヒドロキシメチルメタクリルアミドとメチルメタクリレートとの共重合体、Ｎ－エトキシメチルメタクリルアミドとベンジルメタクリレートとの共重合体、及びＮ－ブトキシメチルアクリルアミドとベンジルメタクリレートと２－ヒドロキシプロピルメタクリレートとの共重合体等が挙げられる。このようなポリマーの重量平均分子量は、１，０００乃至５０，０００であり、好ましくは、１，５００乃至２０，０００であり、より好ましくは２，０００乃至１０，０００である。 Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethyl acrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.
　本発明の感光性樹脂組成物に（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物を含有させる場合の含有量は、（Ａ）成分１００質量部に基づいて５質量部乃至２００質量部であることが好ましく、より好ましくは５０質量部乃至１５０質量部である。この割合が過小である場合には、ネガ型感光性樹脂組成物の光硬化性が低下する場合があり、他方、過大である場合には未露光部の現像性が低下し残膜や残渣の原因となる場合がある。 When the photosensitive resin composition of the present invention contains a compound having two or more functional groups forming a covalent bond with the acid of the component (G), the content is 5% by mass based on 100 parts by mass of the component (A). It is preferably parts to 200 parts by mass, and more preferably 50 parts by mass to 150 parts by mass. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease, while if it is excessive, the developability of the unexposed portion deteriorates and the residual film or residue may be deteriorated. It may be the cause.
＜（Ｈ）成分＞
　（Ｈ）成分は、密着促進剤である。本発明の感光性樹脂組成物は現像後の基板との密着性を向上させる目的で、密着促進剤を添加してもよい。このような密着促進剤の具体例としては、トリメチルクロロシラン、ジメチルビニルクロロシラン、メチルジフェニルクロロシラン、クロロメチルジメチルクロロシラン等のクロロシラン類、トリメチルメトキシシラン、ジメチルジエトキシシラン、メチルジメトキシシラン、ジメチルビニルエトキシシラン、ジフェニルジメトキシシラン、フェニルトリエトキシシラン、ビニルトリクロロシラン、γ－アミノプロピルトリエトキシシラン、γ－メタクリロイルオキシプロピルトリエトキシシラン、γ－メタクリロイルオキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、γ－（Ｎ－ピペリジニル）プロピルトリエトキシシラン、３－ウレイドプロピルトリエトキシシラン、３－ウレイドプロピルトリメトキシシラン等のアルコキシシラン類、ヘキサメチルジシラザン、Ｎ，Ｎ‘‐ビス（トリメチルシリル）ウレア、ジメチルトリメチルシリルアミン、トリメチルシリルイミダゾール等のシラザン類、ベンゾトリアゾール、ベンズイミダゾール、インダゾール、イミダゾール、２－メルカプトベンズイミダゾール、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール、ウラゾール、チオウラシル、メルカプトイミダゾール、メルカプトピリミジン等の複素環状化合物や、１，１－ジメチルウレア、１，３－ジメチルウレア等の尿素、またはチオ尿素化合物を上げることができる。 <(H) component>
The component (H) is an adhesion promoter. The photosensitive resin composition of the present invention may be added with an adhesion accelerator for the purpose of improving the adhesion to the substrate after development. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, and dimethylvinylethoxysilane. Diphenyldimethoxysilane, phenyltriethoxysilane, vinyltrichlorosilane, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ -(N-piperidinyl) propyltriethoxysilane, 3-ureidopropyltriethoxysilane, 3-ureidopropyltrimethoxysilane and other alkoxysilanes, hexamethyldisilazane, N, N'-bis (trimethylsilyl) urea, dimethyltrimethylsilyl Silanes such as amine and trimethylsilylimidazole, benzotriazole, benzimidazole, indazole, imidazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, urazole, thiouracil, mercaptoimidazole, mercaptopyrimidine and the like. Compounds, ureas such as 1,1-dimethylurea and 1,3-dimethylurea, or thiourea compounds can be raised.
　上記の密着促進剤は、例えば、信越化学工業（株）製、Ｍｏｍｅｎｔｉｖｅ　Ｐｅｒｆｏｒｍａｎｃｅ　Ｍａｔｅｒｉａｌｓ　Ｗｏｒｌｄｗｉｄｅ　Ｉｎｃ．製や東レ・ダウコーニング・シリコーン（株）製等の市販品の化合物を用いることもでき、これらの市販品は用意に入手可能である。
　（Ｈ）成分として、前記密着性促進剤のうち１種又は２種類以上を組み合わせて用いることができる。 The above-mentioned adhesion promoter is, for example, manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials World Inc. Commercially available compounds such as those manufactured by Toray Dow Corning Silicone Co., Ltd. and those manufactured by Toray Dow Corning Silicone Co., Ltd. can also be used, and these commercially available products are easily available.
As the component (H), one or a combination of two or more of the adhesion promoters can be used.
　これらの（Ｈ）成分の中、アルコキシシラン類（すなわち、シランカップリング剤）が良好な密着性が得られる点で好ましい。 Among these (H) components, alkoxysilanes (that is, silane coupling agents) are preferable in that good adhesion can be obtained.
　これらの密着促進剤の添加量は、（Ａ）成分の１００質量部に対して、通常、０．１乃至２０質量部、好ましくは０．５乃至１０質量部である。２０質量部以上用いると感度が低下する場合があり、また、０．１質量部未満では密着促進剤の十分な効果が得られない場合がある。 The amount of these adhesion promoters added is usually 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the component (A). If 20 parts by mass or more is used, the sensitivity may decrease, and if it is less than 0.1 parts by mass, a sufficient effect of the adhesion accelerator may not be obtained.
＜その他添加剤＞
　更に、本発明に用いる感光性樹脂組成物は、本発明の効果を損なわない限りにおいて、必要に応じて、レベリング剤、レオロジー調整剤、顔料、染料、保存安定剤、消泡剤、界面活性剤、または多価フェノール、多価カルボン酸等の溶解促進剤等を含有することができる。 <Other additives>
Further, the photosensitive resin composition used in the present invention is, if necessary, a leveling agent, a rheology adjuster, a pigment, a dye, a storage stabilizer, a defoaming agent, and a surfactant, as long as the effects of the present invention are not impaired. , Or a dissolution accelerator such as a polyhydric phenol or a polyvalent carboxylic acid can be contained.
＜感光性樹脂組成物＞
　本発明に用いる感光性樹脂組成物は、下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分を含有する感光性樹脂組成物であり、且つ、所望により、（Ｅ）成分の架橋剤、（Ｆ）成分のエチレン性重合性基を２個以上有する化合物、（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物、（Ｈ）成分の密着促進剤、及びその他添加剤のうち一種以上を更に含有することができる組成物である。
（Ａ）成分：アルカリ可溶性樹脂
（Ｂ）成分：フッ素含有熱分解性重合体
（Ｃ）成分：溶剤
（Ｄ）成分：感光剤 <Photosensitive resin composition>
The photosensitive resin composition used in the present invention is a photosensitive resin composition containing the following components (A), (B), (C) and (D), and if desired, (E). A cross-linking agent for the component, a compound having two or more ethylenically polymerizable groups for the component (F), a compound having two or more functional groups forming a covalent bond with the acid of the component (G), and promoting adhesion of the component (H). It is a composition capable of further containing one or more of the agent and other additives.
(A) component: Alkali-soluble resin (B) component: Fluorine-containing pyrolytic polymer (C) component: Solvent (D) component: Photosensitizer
　本発明に用いる感光性樹脂組成物の好ましい例は、以下のとおりである。
［１］：（Ａ）成分１００質量部に対して０．０１質量部乃至２０質量部の（Ｂ）成分を含有し、これら成分が（Ｃ）成分に溶解された感光性樹脂組成物。
［２］：（Ａ）成分１００質量部に対して０．０１質量部乃至２０質量部の（Ｂ）成分、５質量部乃至１００質量部の（Ｄ）成分を含有し、これら成分が（Ｃ）成分に溶解された感光性樹脂組成物あって、さらに前記（Ｄ）成分が（Ｄ－１）成分である感光性樹脂組成物。
［３］：（Ａ）成分１００質量部に対して０．０１質量部乃至２０質量部の（Ｂ）成分、５質量部乃至１００質量部の（Ｄ）成分を含有し、これら成分が（Ｃ）成分に溶解された感光性樹脂組成物であって、さらに（Ｅ）成分である架橋剤を、（Ａ）成分と（Ｂ）成分の合計の１００質量部に対して１質量部乃至５０質量部含有する感光性樹脂組成物であって、さらに前記（Ｄ）成分が（Ｄ－１）成分である感光性樹脂組成物。
［４］：（Ａ）成分１００質量部に対して０．０１質量部乃至２０質量部の（Ｂ）成分、（Ａ）成分と（Ｂ）成分の合計の１００質量部に対して５乃至２００質量部の（Ｆ）成分、（Ａ）成分と（Ｂ）成分と（Ｆ）成分の合計の１００質量部に対して０．１乃至３０質量部の（Ｄ）成分を含有し、これらが（Ｃ）成分に溶解された感光性樹脂組成物であって、さらに前記（Ｄ）成分が（Ｄ－２）成分である感光性樹脂組成物。 Preferred examples of the photosensitive resin composition used in the present invention are as follows.
[1]: A photosensitive resin composition containing 0.01 part by mass to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and these components are dissolved in the component (C).
[2]: The component (B) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass. A photosensitive resin composition in which the component (D) is a component (D-1).
[3]: The component (B) is contained in an amount of 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A), and the component (D) is contained in an amount of 5 parts by mass to 100 parts by mass. ) The photosensitive resin composition dissolved in the component, and the cross-linking agent which is the component (E) is further added by mass 1 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). A photosensitive resin composition partially contained, wherein the component (D) is a component (D-1).
[4]: 0.01 to 20 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), and 5 to 200 parts by mass of the total of the components (A) and (B). It contains 0.1 to 30 parts by mass of (D) component with respect to 100 parts by mass of the total of (F) component, (A) component, (B) component and (F) component by mass, and these are ( A photosensitive resin composition dissolved in a component (C), wherein the component (D) is a component (D-2).
　本発明に用いる感光性樹脂組成物における固形分の割合は、各成分が均一に溶剤に溶解している限り、特に限定されるものではないが、例えば１質量％乃至８０質量％であり、また例えば５質量％乃至６０質量％であり、または１０質量％乃至５０質量％である。ここで、固形分とは、感光性樹脂組成物の全成分から（Ｃ）成分を除いたものをいう。 The proportion of the solid content in the photosensitive resin composition used in the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1% by mass to 80% by mass. For example, it is 5% by mass to 60% by mass, or 10% by mass to 50% by mass. Here, the solid content refers to a product obtained by removing the component (C) from all the components of the photosensitive resin composition.
　本発明に用いる感光性樹脂組成物の調製方法は、特に限定されないが、その調製法としては、例えば、（Ｂ）成分を（Ｃ）成分に溶解し、この溶液に（Ａ）成分のアルカリ可溶性樹脂、（Ｄ）成分の感光剤、必要に応じて（Ｅ）成分の架橋剤、（Ｆ）成分のエチレン性重合性基を２個以上有する化合物、（Ｇ）成分の酸により共有結合を形成する官能基を２個以上有する化合物、（Ｈ）成分の密着促進剤を所定の割合で混合し、均一な溶液とする方法、或いは、この調製法の適当な段階において、必要に応じてその他添加剤を更に添加して混合する方法が挙げられる。 The method for preparing the photosensitive resin composition used in the present invention is not particularly limited, but as the method for preparing the photosensitive resin composition, for example, the component (B) is dissolved in the component (C) and the component (A) is alkali-soluble in this solution. A covalent bond is formed by a resin, a photosensitizer of component (D), a cross-linking agent of component (E) if necessary, a compound having two or more ethylenically polymerizable groups of component (F), and an acid of component (G). A method of mixing a compound having two or more functional groups and an adhesion promoter of the component (H) in a predetermined ratio to obtain a uniform solution, or adding other substances as necessary at an appropriate stage of this preparation method. Examples thereof include a method of further adding and mixing the agents.
　本発明に用いる感光性樹脂組成物の調製にあたっては、（Ｃ）成分中における重合反応によって得られる共重合体の溶液をそのまま使用することができ、この場合、この（Ｂ）成分の溶液に感光性樹脂組成物の調製のように（Ａ）成分、（Ｄ）成分、必要に応じて（Ｅ）成分、（Ｆ）成分、（Ｇ）成分、（Ｈ）成分などを入れて均一な溶液とする際に、濃度調整を目的としてさらに（Ｃ）成分を追加投入してもよい。このとき、特定共重合体の形成過程で用いられる（Ｃ）成分と、感光性樹脂組成物の調製時に濃度調整のために用いられる（Ｃ）成分とは同一であってもよいし、異なってもよい。 In the preparation of the photosensitive resin composition used in the present invention, the solution of the copolymer obtained by the polymerization reaction in the component (C) can be used as it is, and in this case, it is exposed to the solution of the component (B). Like the preparation of the sex resin composition, the component (A), the component (D), and if necessary, the component (E), the component (F), the component (G), the component (H), etc. are added to form a uniform solution. At the same time, the component (C) may be additionally added for the purpose of adjusting the concentration. At this time, the component (C) used in the process of forming the specific copolymer and the component (C) used for adjusting the concentration at the time of preparing the photosensitive resin composition may be the same or different. May be good.
　而して、調製された感光性樹脂組成物の溶液は、孔径が０．２μｍ程度のフィルタなどを用いて濾過した後、使用することが好ましい。 Therefore, it is preferable that the prepared solution of the photosensitive resin composition is used after being filtered using a filter having a pore size of about 0.2 μm or the like.
＜感光性樹脂組成物により形成される硬化膜＞
　本発明の感光性樹脂組成物は、該組成物を適当な基板（例えば、シリコン／二酸化シリコン被覆基板、シリコンナイトライド基板、金属、例えば、アルミニウム、モリブデン、クロムなどが被覆された基板、ガラス基板、石英基板、ＩＴＯ（Ｉｎｄｉｕｍ　Ｔｉｎ　Ｏｘｉｄｅ、以下ＩＴＯと称す）基板等）やフィルム（例えば、トリアセチルセルロースフィルム、シクロオレフィンポリマーフィルム、シクロオレフィンコポリマーフィルム、ポリエチレンテレフタレートフィルム、ポリエステルフィルム、アクリルフィルム、ポリイミド等の樹脂フィルム）等の基材上に、スピンコート、フローコート、ロールコート、スリットコート、スリットコートに続いたスピンコート、インクジェット法等の方法によって塗布し、その後、ホットプレートまたはオーブン等で予備乾燥することにより、塗膜を形成することができる。その後、この塗膜を加熱処理することにより、下層膜、レジスト膜などとしての感光性樹脂膜が形成される。 <Cured film formed by photosensitive resin composition>
The photosensitive resin composition of the present invention comprises a substrate coated with a suitable substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium, etc., glass substrate). , Quartz substrate, ITO (Indium Tin Oxide, hereinafter referred to as ITO) substrate, etc.) and film (for example, triacetyl cellulose film, cycloolefin polymer film, cycloolefin copolymer film, polyethylene terephthalate film, polyester film, acrylic film, polyimide, etc. (Resin film), etc., is applied by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet method, etc., and then pre-dried with a hot plate or oven. By doing so, a coating film can be formed. Then, by heat-treating this coating film, a photosensitive resin film as an underlayer film, a resist film, or the like is formed.
　この加熱処理の条件としては、例えば、温度７０℃乃至１６０℃、時間０．３乃至６０分間の範囲の中から適宜選択された加熱温度及び加熱時間が採用される。加熱温度及び加熱時間は、好ましくは８０℃乃至１４０℃、０．５乃至１０分間である。 As the conditions for this heat treatment, for example, a heating temperature and a heating time appropriately selected from a temperature range of 70 ° C. to 160 ° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80 ° C. to 140 ° C. and 0.5 to 10 minutes.
　また、感光性樹脂組成物から形成される感光性樹脂膜の膜厚は、例えば０．１μｍ乃至３０μｍであり、また例えば０．２μｍ乃至１０μｍであり、更に例えば０．３μｍ乃至８μｍである。 The film thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 μm to 30 μm, for example, 0.2 μm to 10 μm, and further, for example, 0.3 μm to 8 μm.
　上記で得られた塗膜上に、所定のパターンを有するマスクを装着して紫外線等の光を照射し、アルカリ現像液で現像することで、材料組成により露光部と未露光部のいずれかが洗い出され、残存するパターン状の膜を必要に応じて８０℃乃至１４０℃、０．５乃至１０分間の加熱を行うことで端面のシャープなレリーフパターンが得られる。 By attaching a mask having a predetermined pattern on the coating film obtained above, irradiating it with light such as ultraviolet rays, and developing it with an alkaline developer, either the exposed portion or the unexposed portion is determined depending on the material composition. A sharp relief pattern on the end face can be obtained by heating the washed-out and remaining patterned film at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as needed.
　使用されうるアルカリ性現像液としては、例えば、炭酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化ナトリウムなどのアルカリ金属水酸化物の水溶液、水酸化テトラメチルアンモニウム、水酸化テトラエチルアンモニウム、コリンなどの水酸化第四級アンモニウムの水溶液、エタノールアミン、プロピルアミン、エチレンジアミンなどのアミン水溶液等のアルカリ性水溶液が挙げられる。さらに、これらの現像液には、界面活性剤などを加えることもできる。 Examples of the alkaline developing solution that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, and hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide and choline. Examples thereof include an aqueous solution of quaternary ammonium and an alkaline aqueous solution such as an aqueous solution of amines such as ethanolamine, propylamine and ethylenediamine. Further, a surfactant or the like can be added to these developers.
　上記の中、水酸化テトラエチルアンモニウム０．１乃至２．５８質量％水溶液は、フォトレジストの現像液として一般に使用されており、本発明の感光性樹脂組成物においても、このアルカリ性現像液を用いて、膜の膨潤などの問題をひき起こすことなく良好に現像することができる。 Among the above, a 0.1 to 2.58 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developing solution for a photoresist, and the photosensitive resin composition of the present invention also uses this alkaline developing solution. , It is possible to develop well without causing problems such as swelling of the film.
　また、現像方法としては、液盛り法、ディッピング法、揺動浸漬法など、いずれも用いることができる。その際の現像時間は、通常、１５乃至１８０秒間である。 Further, as the developing method, any of the liquid filling method, the dipping method, the rocking dipping method and the like can be used. The developing time at that time is usually 15 to 180 seconds.
　現像後、感光性樹脂膜に対して流水による洗浄を例えば２０乃至１２０秒間行い、続いて圧縮空気もしくは圧縮窒素を用いてまたはスピニングにより風乾することにより、基板上の水分が除去され、そしてパターン形成された膜が得られる。 After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried with compressed air or compressed nitrogen or by spinning to remove moisture on the substrate and form a pattern. The finished film is obtained.
　続いて、かかるパターン形成膜に対して、熱硬化のためにポストベークを行うことにより、具体的にはホットプレート、オーブンなどを用いて加熱することにより、耐熱性、透明性、平坦化性、低吸水性、耐薬品性などに優れ、良好なレリーフパターンを有する膜が得られる。 Subsequently, the pattern-forming film is post-baked for thermosetting, and specifically, by heating it using a hot plate, an oven, or the like, heat resistance, transparency, flattening property, etc. A film having a good relief pattern with excellent low water absorption and chemical resistance can be obtained.
　ポストベークとしては、一般に、温度１４０℃乃至２７０℃の範囲の中から選択された加熱温度にて、ホットプレート上の場合には５乃至３０分間、オーブン中の場合には３０乃至９０分間処理するという方法が採られる。 Post-baking is generally performed at a heating temperature selected from the temperature range of 140 ° C. to 270 ° C. for 5 to 30 minutes on a hot plate and 30 to 90 minutes in an oven. The method is adopted.
　しかして、かかるポストベークにより、目的とする、良好なパターン形状を有する硬化膜を得ることができる。 Therefore, by such post-baking, the desired cured film having a good pattern shape can be obtained.
　以上のように、硬化膜のパターニング方法により、バンク以外の領域にレジスト材料の成分などの残渣が残りにくいバンクパターンを形成することができ、バンクで区画された領域内に均一な有機薄膜を形成することができる。 As described above, by the method of patterning the cured film, it is possible to form a bank pattern in which residues such as resist material components are unlikely to remain in regions other than the banks, and a uniform organic thin film is formed in the regions partitioned by the banks. can do.
＜ダブルバンクの形成工程＞
　本発明のダブルバンクは、第一バンクと第二バンクを指す。ダブルバンクの形成工程において、第二バンクで区切れ機能を発揮し、第一バンクにより積層される上層材料の濡れ性が向上され、塗布ムラを抑制することができるなら、第一バンクと第二バンクの配置パターンについては特に限定はされない。同様に、第一バンクの濡れ性の向上と第二バンクの区切れ機能を発揮する条件であれば、それぞれのバンクの接触角は限定されない。すなわち、第一バンクの接触角が第二バンクの接触角よりも大きくても良く、小さくても良く、同じでも良い。積層される上層材料の塗布ムラを抑制する観点からは第一バンクの接触角が第二バンクの接触角よりも小さい方が好ましい。 <Double bank formation process>
The double bank of the present invention refers to a first bank and a second bank. In the double bank forming process, if the second bank exerts a separating function, the wettability of the upper layer material laminated by the first bank is improved, and coating unevenness can be suppressed, the first bank and the second bank The arrangement pattern of banks is not particularly limited. Similarly, the contact angle of each bank is not limited as long as the wettability of the first bank is improved and the partitioning function of the second bank is exhibited. That is, the contact angle of the first bank may be larger, smaller, or the same as the contact angle of the second bank. From the viewpoint of suppressing coating unevenness of the upper layer materials to be laminated, it is preferable that the contact angle of the first bank is smaller than the contact angle of the second bank.
　ダブルバンクの形成パターンについていくつか例を挙げる。
　例えば、基板上または他の層上において、第一バンクは、第二バンクに隣接する位置に配置された構造、及び／又は前記第二バンクに囲まれた区域内に孤立して存在するように成す。図４の（ａ）は図３におけるＢ－Ｂ’切断面の模式的な断面図であり、図４の（ａ）に示す第一バンク１３、１４のように、第二バンク２３、２４に隣接する位置に形成される。
　また、基板上において、第一バンクは、第二バンクと交差する構造を成し、第二バンクは第一バンクの上方に直接又は他の層を介して配置された構造を成す。例えば、図１と図２に示すように、第一バンク１１と第二バンク２１、２２と交差するように形成される。図２は図１における構造１００のＡ－Ａ’切断面の断面図であり、図２に示すように、第一バンク１１の上に第二バンク２１、２２が形成される。すなわち、第一バンク１１を形成した後に第二バンク２１、２２が形成される。
　同様に、図４の（ｂ）は図３におけるＣ－Ｃ’切断面の模式的な断面図であり、図４の（ｂ）に示すように、第一バンク１２の上に第二バンク２３、２４が形成される。 Here are some examples of double bank formation patterns.
For example, on a substrate or on another layer, the first bank may be isolated in a structure located adjacent to the second bank and / or in an area surrounded by the second bank. Make up. FIG. 4A is a schematic cross-sectional view of the BB'cut surface in FIG. 3, and the second banks 23 and 24 are shown in the first banks 13 and 14 shown in FIG. 4A. It is formed at an adjacent position.
Further, on the substrate, the first bank has a structure intersecting with the second bank, and the second bank has a structure arranged directly above the first bank or via another layer. For example, as shown in FIGS. 1 and 2, the first bank 11 and the second banks 21 and 22 are formed so as to intersect with each other. FIG. 2 is a cross-sectional view of the AA'cut surface of the structure 100 in FIG. 1, and as shown in FIG. 2, the second banks 21 and 22 are formed on the first bank 11. That is, the second banks 21 and 22 are formed after the first bank 11 is formed.
Similarly, FIG. 4B is a schematic cross-sectional view of the CC'cut surface in FIG. 3, and as shown in FIG. 4B, the second bank 23 is above the first bank 12. , 24 are formed.
　また、第一バンクは、様々なパターンに形成できる。図５は、例として第一バンク及び第二バンクの配置パターンを表す平面図である。１５Ａ、１６Ａ、１６Ａ’は開口部を示し、１５Ｂ、１６Ｂが第一バンクである Also, the first bank can be formed in various patterns. FIG. 5 is a plan view showing an arrangement pattern of the first bank and the second bank as an example. 15A, 16A, 16A'indicate the opening, and 15B, 16B are the first banks.
　上記いずれのダブルバンクの形成工程においても、第一バンクの基板面からの高さは、第二バンクの基板面からの高さよりより低いことには変わらない。 In any of the above double bank forming steps, the height of the first bank from the substrate surface remains lower than the height of the second bank from the substrate surface.
　ここで、図面において、基板上に直接に本発明の感光性樹脂組成物により形成される硬化膜（バンク）しか描かれていないが、あくまでも例である。前記基板上に形成しえる他の層としては、例えば有機エレクトロルミネッセンス素子、ＱＤ－ＯＬＥＤディスプレイやマイクロＬＥＤディスプレイ等があり、例えば有機エレクトロルミネッセンス素子の場合は、陽極、陰極、正孔注入層、正孔輸送層、電子注入層、電子輸送層、電子ブロック層、発光層などの層が挙げられる。本発明のバンク形成する工程において、有機エレクトロルミネッセンス素子に用いられる場合、他の層としては、有機エレクトロルミネッセンス素子の正孔注入層が特に好適である。他の層は、少なくとも１層からなるものである。 Here, in the drawing, only the cured film (bank) formed by the photosensitive resin composition of the present invention is drawn directly on the substrate, but this is just an example. Other layers that can be formed on the substrate include, for example, an organic electroluminescence element, a QD-OLED display, a micro LED display, and the like. For example, in the case of an organic electroluminescence element, an anode, a cathode, a hole injection layer, and a positive layer. Examples thereof include a hole transport layer, an electron injection layer, an electron transport layer, an electron block layer, and a light emitting layer. When used for an organic electroluminescence device in the process of forming a bank of the present invention, the hole injection layer of the organic electroluminescence device is particularly suitable as another layer. The other layer consists of at least one layer.
　以下、実施例を挙げて本発明をさらに詳しく説明するが、本発明は、これら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
［実施例で用いる略記号］
　以下の実施例で用いる略記号の意味は、次のとおりである。
ＭＡＡ：メタクリル酸
ＭＭＡ：メチルメタクリレート
ＨＥＭＡ：２－ヒドロキシエチルメタクリレート
ＣＨＭＩ：Ｎ－シクロヘキシルマレイミド
ＡＩＢＮ：アゾビスイソブチロニトリル
ＰＦＨＭＡ：２－（パーフルオロヘキシル）エチルメタクリレート
ＫＢＭ－５０３：３－メタクリロキシプロピルトリエトキシシラン
ＰＧＭＥ：プロピレングリコールモノメチルエーテル
ＰＧＭＥＡ：プロピレングリコールモノメチルエーテルアセテート
ＱＤ：α、α、α‘－トリス（４－ヒドロキシフェニル）－１－エチル－４－イソプロピルベンゼン１ｍｏｌと１，２－ナフトキノン－２－ジアジド－５－スルホニルクロリド１．５ｍｏｌとの縮合反応によって合成される化合物
ＧＴ－４０１：ブタンテトラカルボン酸テトラ（３，４－エポキシシクロヘキシルメチル）修飾ε－カプロラクトン
ＣＥＬ－２０２１Ｐ：３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート
ＭＰＴＳ：γ－メタクリロキシプロピルトリメトキシシラン
Ｒ－３０：ＤＩＣ（株）製　メガファック　Ｒ－３０（商品名）
Ｒ－４０：ＤＩＣ（株）製　メガファック　Ｒ－４０（商品名） [Abbreviations used in Examples]
The meanings of the abbreviations used in the following examples are as follows.
MAA: MMA Methacrylate: Methyl Methacrylate HEMA: 2-Hydroxyethyl Methacrylate CHMI: N-Cyclohexyl Maleimide AIBN: Azobisisobutyronitrile PFHMA: 2- (Perfluorohexyl) Ethyl Methacrylate KBM-503: 3-Methyloxypropyltri Ethoxysilane PGME: Propyl glycol monomethyl ether PGMEA: Propyl glycol monomethyl ether acetate QD: α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene 1 mol and 1,2-naphthoquinone-2- Compound GT-401 synthesized by condensation reaction with 1.5 mol of diazido-5-sulfonyl chloride: Tetra butanetetracarboxylic acid (3,4-epoxycyclohexylmethyl) modified ε-caprolactone CEL-2021P: 3,4-epoxycyclohexyl Methyl-3', 4'-epoxycyclohexanecarboxylate MPTS: γ-methacryloxypropyltrimethoxysilane R-30: Megafuck R-30 manufactured by DIC Co., Ltd. (trade name)
R-40: Mega Fvck R-40 (trade name) manufactured by DIC Corporation
［数平均分子量及び重量平均分子量の測定］
　以下の合成例に従い得られた特定共重合体及び特定架橋体の数平均分子量及び重量平均分子量を、日本分光（株）製ＧＰＣ装置（Ｓｈｏｄｅｘ（登録商標）カラムＫＦ８０３ＬおよびＫＦ８０４Ｌ）を用い、溶出溶媒テトラヒドロフランを流量１ｍｌ／分でカラム中に（カラム温度４０℃）流して溶離させるという条件で測定した。なお、下記の数平均分子量（以下、Ｍｎと称す。）及び重量平均分子量（以下、Ｍｗと称す。）は、ポリスチレン換算値にて表される。 [Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the specific copolymer and the specific crosslinked product obtained according to the following synthesis examples were determined by using a GPC apparatus manufactured by JASCO Corporation (Shodex® columns KF803L and KF804L) as an elution solvent. The measurement was carried out under the condition that tetrahydrofuran was allowed to flow through the column (column temperature 40 ° C.) at a flow rate of 1 ml / min to elute. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are represented by polystyrene-equivalent values.
＜合成例１＞
　ＭＡＡ　５．０ｇ、ＣＨＭＩ　１１．７ｇ、ＨＥＭＡ　８．３ｇ、ＭＭＡ　８．３ｇ、ＡＩＢＮ　１．７ｇをＰＧＭＥＡ　５２．５ｇに溶解し、温度６０℃乃至１００℃で反応させることにより、アクリル重合体溶液（固形分濃度４０質量％）を得た（Ｐ１）。得られたアクリル重合体のＭｎは４，１００、Ｍｗは７，６００でであった。 <Synthesis example 1>
Acrylic polymer solution by dissolving 5.0 g of MAA, 11.7 g of CHMI, 8.3 g of HEMA, 8.3 g of MMA, and 1.7 g of AIBN in 52.5 g of PGMEA and reacting at a temperature of 60 ° C to 100 ° C. Solid content concentration 40% by mass) was obtained (P1). The obtained acrylic polymer had Mn of 4,100 and Mw of 7,600.
＜合成例２＞
　ＰＦＨＭＡ　５．０ｇ、ＫＢＭ－５０３　３．８ｇ、ＨＥＭＡ　１．５ｇ、ＡＩＢＮ　０．５ｇをＰＧＭＥ　２５．３２ｇに溶解し、８０℃にて２０時間反応させることによりアクリル重合体溶液（固形分濃度３０質量％）を得た（Ｐ２）。得られたアクリル重合体のＭｎは４８００、Ｍｗは６７００であった。 <Synthesis example 2>
Acrylic polymer solution (solid content concentration 30 mass) was obtained by dissolving 5.0 g of PFHMA, 3.8 g of KBM-503, 1.5 g of HEMA, and 0.5 g of AIBN in 25.32 g of PGME and reacting at 80 ° C. for 20 hours. %) Was obtained (P2). The obtained acrylic polymer had Mn of 4800 and Mw of 6700.
＜フッ素含有熱分解性重合体（化合物１）の合成＞
Figure JPOXMLDOC01-appb-C000022
 　国際公開第２０１６／０６３７１９号に記載の公知の方法によりフッ素含有熱分解性重合体（化合物１）を合成した。
　得られた化合物１の分子量は、Ｍｎ２，５００、Ｍｗ２６，０００であった。 <Synthesis of Fluorine-Containing Pyrolytic Polymer (Compound 1)>
Figure JPOXMLDOC01-appb-C000022
 A fluorine-containing pyrolytic polymer (Compound 1) was synthesized by a known method described in International Publication No. 2016/063719.
The molecular weight of the obtained compound 1 was Mn 2,500 and Mw 26,000.
＜実施例１、実施例２、比較例１、比較例２、比較例３、比較例４及び上層膜材料＞
　次の表１に示す組成に従い、実施例の場合は、（Ａ）成分の溶液に、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分を所定の割合で混合し、比較例及び上層膜材料の場合は、（Ａ）成分の溶液に、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分、そして必要に応じて（Ｈ）成分、界面活性剤及び撥液成分を所定の割合で混合し、室温で３時間撹拌して均一な溶液とすることにより、各実施例、各比較例及び上層膜材料のポジ型感光性樹脂組成物を調製した。
（Ａ）成分：アルカリ可溶性樹脂とする特定共重合体
（Ｂ）成分：フッ素含有熱分解性重合体
（Ｃ）成分：溶剤
（Ｄ）成分：感光剤
（Ｅ）成分：アルコキシメチル基またはヒドロキシメチル基を２個以上有する架橋性化合物
（Ｈ）成分：密着促進剤 <Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Upper Membrane Material>
According to the composition shown in Table 1 below, in the case of the example, the component (B), the component (C), the component (D) and the component (E) are mixed in a predetermined ratio with the solution of the component (A). In the case of the comparative example and the upper film material, the solution of the component (A), the component (C), the component (D) and the component (E), and if necessary, the component (H), the surfactant and the liquid repellent component. Was mixed at a predetermined ratio and stirred at room temperature for 3 hours to prepare a uniform solution to prepare a positive photosensitive resin composition for each Example, each Comparative Example and the upper film material.
Component (A): Specific copolymer (B) to be an alkali-soluble resin Component: Fluorine-containing pyrolytic polymer (C) Component: Solvent (D) Component: Photosensitizer (E) Component: alkoxymethyl group or hydroxymethyl Crosslinkable compound (H) component having two or more groups: Adhesion accelerator
　表１に示す組成でポジ型感光性樹脂組成物を調製した。なお、表１中の組成比は固形分での比を表すものとする。 A positive photosensitive resin composition was prepared with the composition shown in Table 1. The composition ratio in Table 1 represents the ratio in terms of solid content.
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
　得られた実施例及び比較例の各ポジ型感光性樹脂組成物を第一バンクとして、得られた上層膜材料１を第一バンクに交差する第二バンクとして、熱硬化時のパターン形状の評価を下記に示す方法で行った。 Evaluation of the pattern shape at the time of thermosetting, with each of the obtained positive photosensitive resin compositions of Examples and Comparative Examples as the first bank and the obtained upper layer film material 1 as the second bank intersecting the first bank. Was carried out by the method shown below.
［パターン形状の評価］
　実施例及び比較例のポジ型感光性樹脂組成物をＩＴＯ－ガラス基板上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が２．２ｍＷ／ｃｍ２の紫外線を列方向に対してライン（５０μｍ）＆スペース（１６０μｍ）パターンが描画されたマスクを介して一定時間照射した。その後０．２質量％の水酸化テトラメチルアンモニウム（以下、ＴＭＡＨと称す）水溶液に６０秒間浸漬することで現像を行い、超純水で３０秒間流水洗浄を行った。次いで、えられた塗膜を温度２３０℃で３０分間加熱することによりポストベークを行い、第一バンクである膜厚約０．５μｍの硬化膜を形成した。
　続いて上層膜材料１を、得られた硬化膜上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い塗膜を形成した。この塗膜にキヤノン（株）製紫外線照射装置ＰＬＡ－６００ＦＡにより３６５ｎｍにおける光強度が２．２ｍＷ／ｃｍ２の紫外線を行方向に対してライン（１００μｍ）＆スペース（５０μｍ）パターンが描画されたマスクを介して一定時間照射した。その後上記と同様にして第一バンクと第二バンクの交差部において、第二バンクである膜厚０．９μｍの硬化膜を形成した。このとき第一バンクと第二バンクの交差部は基板上からの高さが１．４μｍであった。
　作製した列方向に対して延びる５０μｍのラインパターンと行方向に対して延びる１００μｍのラインパターンが交差する箇所のパターン形状を（株）日立ハイテクノロジーズ製電界放出形走査電子顕微鏡Ｓ－４８００を用いて評価した。 [Evaluation of pattern shape]
The positive photosensitive resin compositions of Examples and Comparative Examples were applied onto an ITO-glass substrate using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. A mask in which a line (50 μm) & space (160 μm) pattern is drawn on this coating film with an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., which emits ultraviolet rays having a light intensity of 2.2 mW / cm 2 at 365 nm in the column direction. It was irradiated for a certain period of time through. Then, it was developed by immersing it in a 0.2 mass% tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 60 seconds, and washed with ultrapure water for 30 seconds. Next, the obtained coating film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of about 0.5 μm, which is the first bank.
Subsequently, the upper film material 1 was applied onto the obtained cured film using a spin coater, and then prebaked on a hot plate at a temperature of 110 ° C. for 120 seconds to form a coating film. A mask in which a line (100 μm) & space (50 μm) pattern is drawn on this coating film with an ultraviolet irradiation device PLA-600FA manufactured by Canon Inc., which emits ultraviolet rays having a light intensity of 2.2 mW / cm 2 at 365 nm in the row direction. It was irradiated for a certain period of time through. Then, in the same manner as described above, a cured film having a film thickness of 0.9 μm, which is the second bank, was formed at the intersection of the first bank and the second bank. At this time, the height of the intersection of the first bank and the second bank from the substrate was 1.4 μm.
A field emission scanning electron microscope S-4800 manufactured by Hitachi High-Technologies Corporation was used to determine the pattern shape at the intersection of the 50 μm line pattern extending in the column direction and the 100 μm line pattern extending in the row direction. evaluated.
　以上の評価を行った結果を、次の表２に示す。
Figure JPOXMLDOC01-appb-T000024
 　表２に示すように、実施例１と上層膜材料１から形成したパターン形状及び比較例３と上層膜材料１から形成したパターン形状は、見た目上に特に違いがない。 The results of the above evaluation are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000024
 As shown in Table 2, there is no particular difference in appearance between the pattern shape formed from Example 1 and the upper layer film material 1 and the pattern shape formed from Comparative Example 3 and the upper layer film material 1.
［塗布性の評価］
　続いて、得られた実施例１及び実施例２並びに比較例１、比較例２、比較例３及び比較例４の各感光性樹脂組成物について、それぞれ、Ｓｉウェハ上の塗布性、成膜後（以下、条件１と称す。）の膜の接触角、現像工程を経て成膜した膜（以下、条件２と称す。）の接触角、現像工程を経て成膜した膜にＵＶ／Ｏ３を照射した膜（以下、条件３と称す。）の接触角を各々測定した。 [Evaluation of coatability]
Subsequently, the obtained photosensitive resin compositions of Example 1 and Example 2 and Comparative Example 1, Comparative Example 2, Comparative Example 3 and Comparative Example 4 were coated on a Si wafer and after film formation, respectively. The contact angle of the film (hereinafter referred to as condition 1), the contact angle of the film formed through the developing process (hereinafter referred to as condition 2), and the UV / O 3 applied to the film formed through the developing process. The contact angles of the irradiated membranes (hereinafter referred to as condition 3) were measured.
　実施例及び比較例の感光性樹脂組成物をＳｉウェハ上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．１μｍの感光性樹脂膜を形成した。次いで、得られた感光性樹脂膜をＮａランプ下、目視で観察し、以下の基準で評価した。塗布ムラや塗布スジが観察されない場合は（○）、塗布ムラや塗布スジが観察される場合は（×）であると判断した。 After applying the photosensitive resin compositions of Examples and Comparative Examples onto a Si wafer using a spin coater, prebaking is performed on a hot plate at a temperature of 110 ° C. for 120 seconds to obtain a photosensitive resin film having a film thickness of 1.1 μm. Formed. Next, the obtained photosensitive resin film was visually observed under a Na lamp and evaluated according to the following criteria. When uneven coating or coating streaks were not observed, it was judged to be (◯), and when uneven coating or coating streaks were observed, it was judged to be (x).
［条件１の接触角評価］
　実施例及び比較例の感光性樹脂組成物をＳｉウェハ上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．１μｍの感光性樹脂膜を形成した。次いで、該感光性樹脂膜を温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜上のアニソールの接触角を協和界面科学（株）製の接触角計：Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。 [Evaluation of contact angle under condition 1]
After applying the photosensitive resin compositions of Examples and Comparative Examples onto a Si wafer using a spin coater, prebaking is performed on a hot plate at a temperature of 110 ° C. for 120 seconds to obtain a photosensitive resin film having a film thickness of 1.1 μm. Formed. Next, the photosensitive resin film was post-baked by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm. The contact angle of anisole on this cured film was measured using a contact angle meter: Drop Master manufactured by Kyowa Interface Science Co., Ltd.
［条件２の接触角評価］
　実施例及び比較例の感光性樹脂組成物をＳｉウェハ上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．１μｍの感光性樹脂膜を形成した。次いで、該感光性樹脂膜を０．４質量％の水酸化テトラメチルアンモニウム（以下、ＴＭＡＨと称す）水溶液に９０秒間浸漬した後、超純水で２０秒間流水洗浄を行った。次いで温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した。この硬化膜上のアニソールの接触角を協和界面科学（株）製の接触角計：Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。 [Evaluation of contact angle under condition 2]
After applying the photosensitive resin compositions of Examples and Comparative Examples onto a Si wafer using a spin coater, prebaking is performed on a hot plate at a temperature of 110 ° C. for 120 seconds to obtain a photosensitive resin film having a film thickness of 1.1 μm. Formed. Next, the photosensitive resin film was immersed in a 0.4% by mass tetramethylammonium hydroxide (hereinafter referred to as TMAH) aqueous solution for 90 seconds, and then washed with ultrapure water for 20 seconds. Next, post-baking was performed by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm. The contact angle of anisole on this cured film was measured using a contact angle meter: Drop Master manufactured by Kyowa Interface Science Co., Ltd.
［条件３の接触角評価］
　実施例及び比較例の感光性樹脂組成物をＳｉウェハ上にスピンコーターを用いて塗布した後、温度１１０℃で１２０秒間ホットプレート上においてプリベークを行い、膜厚１．１μｍの感光性樹脂膜を形成した。その後、該感光性樹脂膜を０．４質量％のＴＭＡＨ水溶液に９０秒間浸漬した後、超純水で２０秒間流水洗浄を行った。次いで温度２３０℃で３０分間加熱することによりポストベークを行い、膜厚１．０μｍの硬化膜を形成した後に、テクノビジョン（株）製ＵＶオゾン洗浄装置ＵＶ－３１２を用い１．５Ｊ／ｍ２の紫外線を一定時間照射した。この硬化膜上のアニソールの接触角を協和界面科学（株）製の接触角計：Ｄｒｏｐ　Ｍａｓｔｅｒを用いて測定した。 [Evaluation of contact angle under condition 3]
After applying the photosensitive resin compositions of Examples and Comparative Examples onto a Si wafer using a spin coater, prebaking is performed on a hot plate at a temperature of 110 ° C. for 120 seconds to obtain a photosensitive resin film having a film thickness of 1.1 μm. Formed. Then, the photosensitive resin film was immersed in a 0.4% by mass TMAH aqueous solution for 90 seconds, and then washed with ultrapure water for 20 seconds. Next, post-baking was performed by heating at a temperature of 230 ° C. for 30 minutes to form a cured film having a film thickness of 1.0 μm, and then 1.5 J / m 2 was used with a UV ozone cleaning device UV-312 manufactured by Technovision Co., Ltd. Was irradiated with ultraviolet rays for a certain period of time. The contact angle of anisole on this cured film was measured using a contact angle meter: Drop Master manufactured by Kyowa Interface Science Co., Ltd.
　得られた結果を次の表３に示す。
Figure JPOXMLDOC01-appb-T000025
 The results obtained are shown in Table 3 below.
Figure JPOXMLDOC01-appb-T000025
　表３に示すように、実施例は、塗布性が良好で、硬化膜作製直後から現像工程乃至表面改質工程の有無にかかわらず、接触角は５度以下を示し優れた親液性を保持していた。一方、比較例は、塗布性が良好であったが、硬化膜作製直後は親液性が低下、現像時に感光性樹脂膜表面が洗い流されることによって親液性向上するものの表面改質工程を経ると親液性が低下した。 As shown in Table 3, the examples have good coatability, and the contact angle is 5 degrees or less immediately after the cured film is formed, regardless of the presence or absence of the developing step or the surface modification step, and the excellent liquidity property is maintained. Was. On the other hand, in the comparative example, the coatability was good, but the lipophilicity decreased immediately after the cured film was formed, and the surface of the photosensitive resin film was washed away during development to improve the lipophilicity, but the surface modification step was performed. And the positivity decreased.
１００　構造
２００　構造
１、２　基板
１１、１２、１３、１４、１５、１６　　第一バンク
２１、２２、２３、２４、２５、２６、２７、２８　　第二バンク
１５Ａ　第一バンク１５のＡ区域
１５Ｂ　第一バンク１５のＢ区域
１６Ａ　第一バンク１６のＡ区域
１６Ａ’　第一バンク１６のＡ’区域
１６Ｂ　第一バンク１６のＢ区域 100 Structure 200 Structure 1, 2 Boards 11, 12, 13, 14, 15, 16 First Bank 21, 22, 23, 24, 25, 26, 27, 28 Second Bank 15A First Bank 15 A Area 15B No. B area 16A of one bank 15 A area 16A of the first bank 16'A' area 16B of the first bank 16 B area of the first bank 16

Claims (20)

  1. 　第一バンクと第二バンクとを基板上に直接もしくは他の層を介して配設することにより、個々の画素域が画定されている表示素子において第一バンクの材料として適用される組成物であって、
    　下記（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分を含有する感光性樹脂組成物。
    （Ａ）成分：アルカリ可溶性樹脂
    （Ｂ）成分：フッ素含有熱分解性重合体
    （Ｃ）成分：溶剤
    （Ｄ）成分：感光剤     A composition that is applied as a material for the first bank in a display device in which individual pixel areas are defined by arranging the first bank and the second bank directly on the substrate or via another layer. There,
    A photosensitive resin composition containing the following components (A), (B), (C) and (D).
    (A) component: Alkali-soluble resin (B) component: Fluorine-containing pyrolytic polymer (C) component: Solvent (D) component: Photosensitizer
  2. 　基板上において、前記第一バンクは、前記第二バンクに隣接する位置に配置された構造、及び／又は前記第二バンクに囲まれた区域内に孤立して存在する構造、及び／又は前記第二バンクと交差する構造を成し、
    　そして、前記第一バンクの基板面からの高さは、前記第二バンクの基板面からの高さよりもより低い請求項１に記載の感光性樹脂組成物。     On the substrate, the first bank has a structure arranged adjacent to the second bank and / or a structure isolated in an area surrounded by the second bank, and / or the first bank. It has a structure that intersects with two banks,
    The photosensitive resin composition according to claim 1, wherein the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface.
  3. 　基板上において、前記第二バンクは、前記第一バンクの上方に直接もしくは他の層を介して配置された構造を成し、
    　そして、前記第一バンクの基板面からの高さは、前記第二バンクの基板面からの高さよりもより低い請求項１に記載の感光性樹脂組成物。     On the substrate, the second bank forms a structure arranged directly above the first bank or via another layer.
    The photosensitive resin composition according to claim 1, wherein the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface.
  4. 　前記（Ｂ）成分であるフッ素含有熱分解性重合体は、重合性単量体の重合体構造を有する主鎖（ａ）と、下記一般式（１）で表される官能基を有する側鎖（ｂ）を有するフッ素含有熱分解性重合体である請求項１乃至請求項３のいずれか一項に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１、Ｒ２及びＲ３はそれぞれ独立して水素原子または炭素原子数１～１８の有機基であり、Ｒ４はフッ素化アルキル基又はポリ（パーフルオロアルキレンエーテル）鎖である。Ｙ１は酸素原子または硫黄原子である。）     The fluorine-containing pyrolytic polymer, which is the component (B), has a main chain (a) having a polymer structure of a polymerizable monomer and a side chain having a functional group represented by the following general formula (1). The photosensitive resin composition according to any one of claims 1 to 3, which is a fluorine-containing pyrolytic polymer having (b).
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 , R 2 and R 3 are independently hydrogen atoms or organic groups having 1 to 18 carbon atoms, and R 4 is a fluorinated alkyl group or a poly (perfluoroalkylene ether) chain. . Y 1 is an oxygen atom or a sulfur atom.)
  5. 　前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が１～６のフッ素化アルキル基である請求項１乃至請求項４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein R 4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded.
  6. 　前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が４～６のフッ素化アルキル基である請求項１乃至請求項４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 4, wherein R 4 is a fluorinated alkyl group having 4 to 6 carbon atoms to which a fluorine atom is directly bonded.
  7. 　前記Ｒ１、Ｒ２およびＲ３がそれぞれ独立して水素原子であり、前記Ｒ４が、フッ素原子が直接結合した炭素原子の数が１～６のフッ素化アルキル基である請求項１乃至請求項４のいずれか一項に記載の感光性樹脂組成物。 Claims 1 to 6 , wherein R 1 , R 2 and R 3 are independently hydrogen atoms, and R 4 is a fluorinated alkyl group having 1 to 6 carbon atoms to which a fluorine atom is directly bonded. Item 2. The photosensitive resin composition according to any one of Item 4.
  8. 　前記一般式（１）で表される側鎖（ｂ）が、下記式（１－１）で表されるものである請求項１乃至請求項４のいずれか一項に記載の感光性樹脂組成物。
    Figure JPOXMLDOC01-appb-C000002
         The photosensitive resin composition according to any one of claims 1 to 4, wherein the side chain (b) represented by the general formula (1) is represented by the following formula (1-1). Stuff.
    Figure JPOXMLDOC01-appb-C000002
  9. 　前記感光性樹脂組成物は、下記（Ｚ１）乃至（Ｚ４）のうち少なくともいずれか１つを満足する請求項１乃至請求項８のいずれか一項に記載の感光性樹脂組成物。
    　（Ｚ１）：（Ｅ）成分である架橋剤をさらに含有する
    　（Ｚ２）：前記アルカリ可溶性樹脂が、自己架橋性基をさらに有するか、又はヒドロキシ基、カルボキシル基、アミド基及びアミノ基からなる群から選ばれる少なくとも１つの基と反応する基をさらに有する
    　（Ｚ３）：前記感光剤が光ラジカル発生剤であり、さらに、（Ｆ）成分としてエチレン性二重結合を２個以上有する化合物を含有する
    　（Ｚ４）：前記感光剤が光酸発生剤であり、さらに、（Ｇ）成分として前記光酸発生剤より発生した酸により共有結合を形成する官能基を２個以上有する化合物を含有する     The photosensitive resin composition according to any one of claims 1 to 8, wherein the photosensitive resin composition satisfies at least one of the following (Z1) to (Z4).
    (Z1): Further contains a cross-linking agent as a component (E) (Z2): The alkali-soluble resin further has a self-cross-linking group or is a group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group. Further having a group that reacts with at least one group selected from (Z3): The photosensitive agent is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as the component (F). (Z4): The photosensitizer is a photoacid generator, and further contains, as a component (G), a compound having two or more functional groups forming a covalent bond with the acid generated from the photoacid generator.
  10. 　前記感光剤がキノンジアジド化合物である請求項１乃至請求項９のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 9, wherein the photosensitive agent is a quinonediazide compound.
  11. 　前記感光剤がキノンジアジド化合物であり、さらに、前記（Ｚ１）又は（Ｚ２）のいずれかを満足する請求項９に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 9, wherein the photosensitive agent is a quinonediazide compound, and further satisfies either (Z1) or (Z2).
  12. 　前記感光剤がジアゾナフトキノンである請求項１１に記載の感光性樹脂組成物。 The photosensitive resin composition according to claim 11, wherein the photosensitive agent is diazonaphthoquinone.
  13. 　前記アルカリ可溶性樹脂の数平均分子量がポリスチレン換算で２，０００乃至５０，０００である請求項１乃至請求項１２のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 12, wherein the alkali-soluble resin has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
  14. 　前記アルカリ可溶性樹脂１００質量部に対して０．０１質量部乃至１質量部の前記フッ素含有熱分解性重合体を含有する請求項１乃至請求項１３のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 13, which contains 0.01 parts by mass to 1 part by mass of the fluorine-containing pyrolytic polymer with respect to 100 parts by mass of the alkali-soluble resin. Stuff.
  15. 　前記アルカリ可溶性樹脂１００質量部に対して、前記架橋剤が１質量部乃至５０質量部である請求項９乃至請求項１４のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 9 to 14, wherein the cross-linking agent is 1 part by mass to 50 parts by mass with respect to 100 parts by mass of the alkali-soluble resin.
  16. 　前記第二バンクと前記第一バンクで画定された画素域に有機薄膜を備える表示素子において、前記有機薄膜が有機エレクトロルミネッセンス素子の画素に用いる請求項１乃至請求項１５のいずれか一項に記載の感光性樹脂組成物。 The invention according to any one of claims 1 to 15, wherein the display element includes the organic thin film in the pixel area defined by the second bank and the first bank, and the organic thin film is used for the pixels of the organic electroluminescence element. Photosensitive resin composition.
  17. 　前記他の層が有機エレクトロルミネッセンス素子の正孔注入層である請求項１乃至請求項１６のいずれか一項に記載の感光性樹脂組成物。 The photosensitive resin composition according to any one of claims 1 to 16, wherein the other layer is a hole injection layer of an organic electroluminescence device.
  18. 　請求項１乃至請求項１７のいずれか一項に記載の感光性樹脂組成物により形成された硬化膜。 A cured film formed by the photosensitive resin composition according to any one of claims 1 to 17.
  19. 　請求項１８に記載の硬化膜を有する表示素子。 A display element having the cured film according to claim 18.
  20. 　第一バンクを基板上に直接もしくは他の層を介して形成する工程と、
    　第二バンクを基板上に直接もしくは他の層を介して形成する工程とを含み、
    　前記第一バンクは、請求項１乃至請求項１７のいずれ一項に記載の感光性樹脂組成物からなる、個々の画素域が画定されている表示素子の製造方法。     The process of forming the first bank directly on the substrate or via other layers,
    Including the step of forming the second bank directly on the substrate or via other layers.
    The first bank is a method for manufacturing a display element in which individual pixel regions are defined, which comprises the photosensitive resin composition according to any one of claims 1 to 17.
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JP2017049327A (en) * 2015-08-31 2017-03-09 富士フイルム株式会社 Photosensitive composition, method for manufacturing cured film, method for manufacturing liquid crystal display device, method for manufacturing organic electroluminescence display device, and method for manufacturing touch panel
JP2017142475A (en) * 2016-02-10 2017-08-17 Dic株式会社 Colored curable resin composition and cured film thereof

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