WO2014125884A1 - Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile - Google Patents

Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile Download PDF

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WO2014125884A1
WO2014125884A1 PCT/JP2014/051249 JP2014051249W WO2014125884A1 WO 2014125884 A1 WO2014125884 A1 WO 2014125884A1 JP 2014051249 W JP2014051249 W JP 2014051249W WO 2014125884 A1 WO2014125884 A1 WO 2014125884A1
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group
carbon atoms
resin composition
photosensitive resin
compound
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PCT/JP2014/051249
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English (en)
Japanese (ja)
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谷垣勇剛
藤原健典
諏訪充史
福原将
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東レ株式会社
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Priority to CN201480008215.6A priority Critical patent/CN104981737A/zh
Priority to JP2014503896A priority patent/JP6319082B2/ja
Priority to KR1020157017378A priority patent/KR20150118582A/ko
Publication of WO2014125884A1 publication Critical patent/WO2014125884A1/fr

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    • 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
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a photosensitive resin composition, a protective film or an insulating film obtained by thermosetting it, a touch panel using the same, and a method for manufacturing the same.
  • the sensor substrate of the capacitive touch panel has wiring in which ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, or the like) is patterned on glass.
  • ITO Indium Tin Oxide
  • metal silver, molybdenum, aluminum, or the like
  • an insulating film, ITO A structure having a protective film for protecting a metal is common.
  • the protective film is formed of high-hardness inorganic SiO 2 or SiN x or a photosensitive transparent material (Patent Document 1), and the insulating film is often formed of a photosensitive transparent material.
  • inorganic materials are formed by forming a high temperature film of SiO 2 or SiN x by CVD (Chemical Vapor Deposition), and increasing the number of processes due to pattern processing using resist. was there. Furthermore, it has poor moisture and heat resistance, and the underlying metal wiring corrodes, making it impossible to obtain a highly reliable touch panel.
  • CVD Chemical Vapor Deposition
  • Photosensitive transparent materials can be expected to reduce costs by reducing the number of processes, but the hardness is insufficient and the heat and heat resistance is low, as with inorganic materials. I had it. Furthermore, in the reliability test, it is also required to suppress corrosion of the underlying metal wiring due to the infiltration of the artificial sweat solution.
  • the cured film obtained from the photosensitive transparent material is exposed to various acidic or alkaline chemicals such as an etching solution for processing ITO or the underlying metal wiring, but if the cured film has low chemical resistance, Peeling or floating occurs at the interface between the cured film and the underlying metal wiring or substrate, which may cause ITO disconnection.
  • the cured film obtained from the photosensitive transparent material is exposed to a high vacuum state during the ITO film formation. However, if the resistance to vacuum is low, the cured film changes in quality due to outgas from the cured film and the substrate. Cause lowering of adhesion.
  • the coating liquid of the photosensitive transparent material was stored at room temperature, the material was altered during storage, and there was a problem that the adhesion with the substrate was lowered. Therefore, it has high hardness, transparency, moisture and heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance, pattern processing with alkaline developer, and storage stability of coating liquid is good. There has been a strong demand for a photosensitive transparent material in which adhesiveness does not decrease.
  • a photosensitive transparent material containing a polyfunctional epoxy compound (Patent Document 3), a photosensitive transparent material containing a metal chelate compound such as a zirconium compound (Patent Document 4), maleimide A photosensitive transparent material (Patent Document 5) containing an acrylic resin having a structure derived from, or a photosensitive transparent material (Patent Document 6) containing a triazine compound has been developed.
  • the cured film obtained has high hardness, excellent transparency, moisture and heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance, and can be patterned with an alkaline developer, and stable storage of the coating liquid.
  • the present invention is capable of obtaining a cured film having high hardness, excellent transparency, moisture and heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance, and storage stability of the coating liquid.
  • An object of the present invention is to provide a photosensitive resin composition that can be alkali developed and has a plurality of performances that are good and that adhesion does not decrease during storage.
  • the present invention is a photosensitive resin composition containing (A) an acrylic resin, (B) a radical polymerizable compound, (C) a photopolymerization initiator, (D) a metal chelate compound, and (E) a solvent.
  • the (A) acrylic resin provides a photosensitive resin composition having a structure derived from maleimide having a specific structure.
  • the photosensitive resin composition of the present invention it is possible to obtain a cured film having high hardness and excellent transparency, moisture and heat resistance, artificial sweat resistance, adhesion, chemical resistance and vacuum resistance.
  • the photosensitive resin composition of the present invention it is possible to prepare a coating liquid that has good storage stability and does not deteriorate adhesion during storage.
  • the photosensitive resin composition of the present invention contains (A) an acrylic resin, (B) a radical polymerizable compound, (C) a photopolymerization initiator, (D) a metal chelate compound, and (E) a solvent, (A)
  • the acrylic resin has a structure derived from maleimide represented by the general formula (1).
  • the photosensitive resin composition of the present invention contains (A) an acrylic resin.
  • the acrylic resin Since the acrylic resin has a structure derived from maleimide represented by the general formula (1), the hardness, chemical resistance, and vacuum resistance of the cured film obtained without impairing the storage stability of the coating liquid, Moisture heat resistance, artificial sweat resistance and heat resistance can be improved.
  • the acrylic resin does not have this structure, the storage stability of the coating liquid is poor, the reaction proceeds during storage of the coating liquid, the photosensitive resin composition is altered, and the chemical resistance or adhesion is It will decline. From this, it is presumed that the structure contributes to stabilization and suppresses the progress of the reaction.
  • (A) the acrylic resin has this structure, the reaction at the time of thermosetting is promoted and the crosslinking density is improved, and the hardness, vacuum resistance, moist heat resistance and artificial sweat resistance of the resulting cured film are improved. Is done. Furthermore, it is considered that the chemical resistance of the resulting cured film is improved by the function of the structure as a site that can be coordinated to the underlying substrate surface.
  • the acrylic resin preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton in the structure. It is considered that the chemical resistance, vacuum resistance, heat and humidity resistance, artificial sweat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity and chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton.
  • X is a direct bond, an alkylene chain having 1 to 6 carbon atoms, a cycloalkylene chain having 4 to 7 carbon atoms, or the number of carbon atoms 6-10 arylene chains are preferred.
  • R 1 is hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • an ester group or a hydroxy group having 2 to 7 carbon atoms hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 6 to 10 carbon atoms.
  • an aryl group, an ester group having 2 to 5 carbon atoms, or a hydroxy group are more preferably an aryl group, an ester group having 2 to 5 carbon atoms, or a hydroxy group.
  • R 1 is an aryl group having 6 to 15 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyloxy group having 2 to 7 carbon atoms, an ester group having 2 to 7 carbon atoms, a hydroxy group Group or carboxy group, preferably an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an ester group having 2 to 5 carbon atoms, a hydroxy group or a carboxy group. More preferred.
  • R 1 is an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an ester group having 2 to 7 carbon atoms, a hydroxy group A carboxy group, an amino group or a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an ester group having 2 to 5 carbon atoms, a hydroxy group, A carboxy group, an amino group or a nitro group is more preferred.
  • alkylene chain, cycloalkylene chain, arylene chain, alkyl group, cycloalkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, ester group and amino group are either unsubstituted or substituted. It doesn't matter.
  • the content ratio of the structure derived from the maleimide represented by the general formula (1) in the acrylic resin is determined by the hardness, chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, heat resistance improvement and coating of the cured film. From the viewpoint of improving the storage stability of the liquid, it is preferably 5 to 80 mol%, more preferably 7 to 70 mol%, still more preferably 10 to 60 mol%.
  • the acid value of the acrylic resin is preferably 40 to 200 mgKOH / g, more preferably 50 to 180 mgKOH / g, and still more preferably 70 to 140 mgKOH / g.
  • the acid value represents the weight of KOH that reacts with an acidic group in 1 g of the resin, and the unit is mgKOH / g. From the acid value, the number of acidic groups in the resin can be determined.
  • the acid value is in the above range, the residue of the photosensitive resin composition after development with an alkaline developer can be suppressed, and the film thickness reduction in the exposed area can be suppressed, and a good pattern can be formed.
  • the double bond equivalent of the acrylic resin is preferably 150 to 10,000 g / mol, more preferably 200 to 5,000 g / mol, and still more preferably 250 to 2,000 g / mol.
  • the double bond equivalent represents the resin weight per 1 mol of unsaturated groups, and the unit is g / mol.
  • the double bond equivalent can be calculated by measuring the iodine value. When the double bond equivalent is in the above range, the hardness and crack resistance of the cured film can be compatible at a high level.
  • the weight average molecular weight (Mw) of the acrylic resin is preferably 2,000 to 100,000, more preferably 5,000 to 40,000 in terms of polystyrene measured by gel permeation chromatography (GPC). preferable.
  • GPC gel permeation chromatography
  • (A) As the acrylic resin those obtained by radical copolymerization of maleimide or a maleimide derivative, a (meth) acrylic compound having a carboxy group or an acid anhydride group, and other (meth) acrylic acid esters are preferable.
  • the radical polymerization initiator used for radical copolymerization include azo compounds such as 2,2′-azobis (isobutyronitrile) and 2,2′-azobis (2,4-dimethylvaleronitrile), or lauroyl peroxide.
  • Organic peroxides such as di-t-butyl peroxide, bis (4-tert-butylcyclohexane-1-yl) peroxydicarbonate, t-butyl 2-ethylperoxyhexanoate, methyl ethyl ketone peroxide, benzoyl peroxide or cumene hydroperoxide An oxide etc. are mentioned.
  • the conditions for radical copolymerization can be appropriately set. For example, after sufficiently purging the inside of the reaction vessel with nitrogen by bubbling or vacuum degassing, a copolymer component and a radical polymerization initiator are added in a solvent, and 60 The reaction is preferably carried out at ⁇ 110 ° C. for 30 to 500 minutes. When a (meth) acrylic compound having an acid anhydride group is used as a copolymerization component, it is preferable to add a theoretical amount of water and react at 30 to 60 ° C. for 30 to 60 minutes. Moreover, you may use chain transfer agents, such as a thiol compound, as needed.
  • maleimides or maleimide derivatives include maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Nn -Hexylmaleimide, N-dodecylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N- (2,4-dimethylcyclohexyl) maleimide, N-vinylmaleimide, N- (meth) acrylmaleimide, N-methoxymethylmaleimide, N- (2-ethoxyethyl) maleimide, N- (4-butoxyethyl) maleimide, N-[(meth) acryloxymethyl] maleimide, N- [2- (meth) acryloxyethyl] maleimide, N- [3 -(Meth) acryloxypro Lu]
  • Examples of the (meth) acrylic compound having a carboxy group or an acid anhydride group include (meth) acrylic acid, (meth) acrylic anhydride, itaconic acid, itaconic anhydride, mono (2-acryloxyethyl) succinate. ), Mono (2-acryloxyethyl) phthalate or mono (2-acryloxyethyl) tetrahydrophthalate.
  • (meth) acrylic acid esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth ) Cyclohexyl acrylate, cyclohexenyl (meth) acrylate, (4-methoxy) cyclohexyl (meth) acrylate, (2-isopropyloxycarbonyl) ethyl (meth) acrylate, (meth) acrylic acid (2-cyclopentyloxycarbonyl) ) Ethyl, (meth) acrylic acid (2-cyclohexyloxycarbonyl) ethyl, (meth) acrylic acid (2-cyclohexylenylcarbonyl) ethyl, (meth) acrylic acid [2- (4-methoxycyclohexyl) oxycarbonyl]
  • aromatic vinyl compounds such as styrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene or ⁇ -methylstyrene may be used.
  • Styrene is preferably used because it improves vacuum resistance, heat and humidity resistance, artificial sweat resistance and heat resistance.
  • Acrylic resin having an ethylenically unsaturated double bond group is a radical copolymer of maleimide or maleimide derivative, (meth) acrylic compound having carboxy group or acid anhydride group and other (meth) acrylic acid ester. Furthermore, what is obtained by ring-opening addition reaction of an epoxy group-containing unsaturated compound having an ethylenically unsaturated double bond group is preferable. Examples of the catalyst used for the ring-opening addition reaction of an epoxy group-containing unsaturated compound include triethylamine, dimethylaniline, tetramethylethylenediamine, 2,4,6-tris (dimethylaminomethyl) phenol, dimethylbenzylamine, or tri-n-.
  • Amine-based catalysts such as octylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium fluoride, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, bis (2 -Tin-based catalysts such as ethylhexanoic acid) tin (II) or di-n-butyltin (IV) dilaurate, titanium-based catalysts such as tetrakis (2-ethylhexanoic acid) titanium (IV), triphenyl Phosphorus-based catalysts such as phosphine or triphenylphosphine oxide, chromium-based catalysts such as tris (acetylacetonato) chromium (III), chromium (III) chloride, chromium (III) o
  • epoxy group-containing unsaturated compound examples include glycidyl (meth) acrylate, ( ⁇ -ethyl) glycidyl (meth) acrylate, (meth) acrylic acid ( ⁇ -n-propyl) glycidyl, (meth) acrylic acid ( ⁇ -n-butyl) glycidyl, (meth) acrylic acid (3,4-epoxy) n-butyl, (meth) acrylic acid (3,4-epoxy) heptyl, (meth) acrylic acid ( ⁇ -ethyl-6, 7-epoxy) heptyl, allyl glycidyl ether, vinyl glycidyl ether, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl ether, ⁇ -methyl-2-vinylbenzyl glycidyl ether, ⁇ -
  • the content of the (A) acrylic resin in the photosensitive resin composition of the present invention is such that when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight, the hardness of the cured film, From the viewpoint of chemical resistance, vacuum resistance, heat and humidity resistance, artificial sweat resistance, heat resistance improvement and storage stability improvement of coating liquid, it is preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight, and 30 to 60 parts by weight. Is more preferable.
  • the photosensitive resin composition of the present invention may further contain (A) an acrylic resin other than the acrylic resin.
  • an acrylic resin it is preferable that an acid value, a double bond equivalent, and a weight average molecular weight (Mw) are in the same range as (A) acrylic resin, respectively.
  • About radical polymerization initiator used for radical copolymerization, conditions for radical copolymerization, (meth) acrylic compound having carboxy group or acid anhydride group, (meth) acrylic acid ester and aromatic vinyl compound as other copolymerization component Can be the same as (A) when obtaining an acrylic resin.
  • the catalyst used for the ring-opening addition reaction of the epoxy group-containing unsaturated compound and the epoxy group-containing unsaturated compound can be the same as in the case of obtaining the acrylic resin (A) having an ethylenically unsaturated double bond group. .
  • the content of acrylic resin other than (A) acrylic resin in the photosensitive resin composition of the present invention is the total of (A) acrylic resin, (B) radical polymerizable compound, and (A) acrylic resin other than acrylic resin.
  • A acrylic resin other than acrylic resin.
  • 100 parts by weight 1 to 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable.
  • the photosensitive resin composition of the present invention contains (B) a radical polymerizable compound.
  • the radically polymerizable compound refers to a compound having a plurality of ethylenically unsaturated double bond groups in the molecule, but is preferably a radically polymerizable compound having a (meth) acrylic group that facilitates radical polymerization. .
  • the radicals generated from the photopolymerization initiator (C) described later the polymerization of the (B) radical polymerizable compound proceeds, the exposed portion of the photosensitive resin composition is insolubilized in the alkaline aqueous solution, A pattern can be formed.
  • the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol from the viewpoints of sensitivity at the time of exposure and hardness of the cured film.
  • radical polymerizable compound examples include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, 1,3-butanediol di (meth) acrylate, neopentyl glycol di ( (Meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1 10-decanediol di (meth)
  • the content of the (B) radical polymerizable compound in the photosensitive resin composition of the present invention is 20 to 90 weights when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight.
  • it is preferably 30 to 80 parts by weight, and more preferably 40 to 70 parts by weight.
  • the photosensitive resin composition of the present invention contains (C) a photopolymerization initiator.
  • C As a photoinitiator, what generate
  • Examples of the (C) photopolymerization initiator include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl)- 1- (4-morpholinophenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 3,6-bis (2-methyl-2) ⁇ -aminoalkylphenone compounds such as -morpholinopropionyl) -9-octyl-9H-carbazole, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide or Bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) phosphine oxide Any acylphosphine oxide compound, 1-phenylpropane
  • an ⁇ -aminoalkylphenone compound an acylphosphine oxide compound, an oxime ester compound, a benzophenone compound having an amino group, or A benzoic acid ester compound having an amino group is preferred.
  • benzophenone compound having an amino group examples include 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone.
  • benzoic acid ester compound having an amino group examples include ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid (2-ethylhexyl), and ethyl 4-diethylaminobenzoate.
  • the content of the (C) photopolymerization initiator in the photosensitive resin composition of the present invention is 0.1-0.1% when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. 20 parts by weight is preferable, and 1 to 10 parts by weight is more preferable.
  • the photosensitive resin composition of the present invention contains (D) a metal chelate compound.
  • D By containing a metal chelate compound, the chemical resistance, vacuum resistance, heat-and-moisture resistance, and artificial sweat resistance of the obtained cured film can be improved. This is presumably because the metal chelate compound reacts with a resin or the like by heat and is taken in as a part of a three-dimensional network structure formed during thermosetting. In other words, since relatively large atoms are taken into the cured film, the film density of the cured film increases, and the permeability of moisture and chemicals decreases. It is thought that heat resistance and artificial sweat resistance are improved.
  • metal chelate compounds include titanium chelate compounds, zirconium chelate compounds, aluminum chelate compounds, magnesium chelate compounds, zinc chelate compounds, indium chelate compounds, tin chelate compounds, and copper chelate compounds.
  • a titanium chelate compound, a zirconium chelate compound, an aluminum chelate compound or a magnesium chelate compound is preferable, and from the viewpoint of moisture resistance and artificial sweat resistance of the cured film, a zirconium chelate compound is more preferable.
  • metal chelate compounds can be easily obtained by reacting a metal alkoxide with a chelating agent.
  • a chelating agent examples include ⁇ -diketones such as acetylacetone, benzoylacetone or dibenzoylmethane, or ⁇ -ketoesters such as ethyl acetoacetate or ethyl benzoylacetate.
  • metal chelate compound (D) examples include tetrakis (acetylacetonato) titanium (IV), diisopropoxybis (ethylacetoacetate) titanium (IV), and diisopropoxybis (acetylacetonato) titanium (IV).
  • the metal chelate compound is preferably a compound represented by the general formula (2).
  • R 2 represents hydrogen, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms
  • R 3 and R 4 are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.
  • R 2 is preferably hydrogen, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, or an aryl group having 6 to 10 carbon atoms
  • R 3 and R 4 are each independently hydrogen
  • An alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group is preferable.
  • the alkyl group, cycloalkyl group, aryl group, and alkoxy group may be either unsubstituted or substituted.
  • M is preferably zirconium.
  • Examples of the compound represented by the general formula (2) include tetrakis (acetylacetonato) titanium (IV), diisopropoxybis (ethylacetoacetate) titanium (IV), and diisopropoxybis (acetylacetonate).
  • Titanium chelate compounds such as titanium (IV), tetrakis (acetylacetonato) zirconium (IV), di-n-butoxybis (ethylacetoacetate) zirconium (IV) or tri-n-butoxymono (acetylacetonato) zirconium (IV
  • Zirconium chelate compounds such as tris (acetylacetonate) aluminum (III), tris (ethylacetoacetate) aluminum (III), mono (acetylacetonato) bis (ethylacetoacetate) aluminum (II) ),
  • An aluminum chelate compound such as diisopropoxymono (ethylacetoacetate) aluminum (III) or Preneact (registered trademark) AL-M (manufactured by Kawaken Fine Chemical Co., Ltd.) or bis (acetylacetonato) magnesium (II)
  • magnesium chelate compounds such as bis (ethylacetoacetate) magnesium (I
  • the content of the (D) metal chelate compound in the photosensitive resin composition of the present invention is 0.1 to 10 when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. Part by weight is preferable, and 0.5 to 5 parts by weight is more preferable. (D) If the content of the metal chelate compound is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance or artificial sweat resistance may be insufficient. On the other hand, if it exceeds 10 parts by weight, it may cause a decrease in transparency and a residue after development, and the storage stability of the coating liquid may decrease.
  • the photosensitive resin composition of the present invention contains (E) a solvent.
  • E) a solvent each component can be melt
  • a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable.
  • the solvent is appropriately volatilized at the time of coating, and the coating film is dried, so that a good coating film with no coating unevenness can be obtained.
  • the boiling point to 250 ° C. or lower, it is possible to suppress the amount of solvent remaining in the coating film and to reduce the amount of film shrinkage at the time of thermosetting, so that better flatness can be obtained.
  • Examples of the compound having an alcoholic hydroxyl group and a boiling point of 110 to 250 ° C. under atmospheric pressure include hydroxyacetone, 4-hydroxy-2-butanone, 3-hydroxy-3-methyl-2-butanone, 4- Hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl lactate, ethyl lactate, lactic acid n-propyl, n-butyl lactate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propi Glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-t-butyl ether, diethylene glycol
  • diacetone alcohol ethyl lactate, ethylene glycol monomethyl ether, propylene glycol mono Chirueteru, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methyl-1-butanol or tetrahydrofurfuryl alcohol.
  • Examples of the compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include, for example, n-butyl acetate, isobutyl acetate, 3-methoxy-n-butyl acetate, 3-methyl-3-methoxy-n -Butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, methyl n-butyl ketone, methyl isobutyl ketone, diisobutyl ketone, 2-heptanone, acetylacetone, cyclopentanone, cyclohexanone, cycloheptanone, ⁇ -butyrolactone, ⁇ - Examples include valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, N, N′-dimethylformamide, N, N′-dimethylacetamide, or 1,3-dimethyl-2-
  • Examples of the compound having three or more ether bonds and a boiling point of 110 to 250 ° C. under atmospheric pressure include diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol di-n-propyl ether, dipropylene glycol.
  • Examples thereof include dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol ethyl methyl ether and dipropylene glycol di-n-propyl ether. From the viewpoint of applicability, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether or dipropylene glycol dimethyl ether is preferable.
  • the content of the solvent (E) in the photosensitive resin composition of the present invention may be appropriately adjusted according to the coating method and the like.
  • the photosensitive resin composition Generally, it is 50 to 95% by weight of the whole.
  • the photosensitive resin composition of the present invention is further selected from the group consisting of (F) amino group, amide group, ureido group, ketimine group, isocyanate group, mercapto group, isocyanuric ring skeleton, (meth) acryl group and styryl group. It is preferable to contain the silane compound which has a substituent (henceforth "(F) silane compound"). (F) It is preferable that a silane compound has an alkoxy group from a viewpoint of the adhesiveness of a cured film. When the photosensitive resin composition contains the (F) silane compound, the adhesion and chemical resistance of the resulting cured film can be improved.
  • some functional groups function as sites that can be coordinated to the underlying substrate surface.
  • the alkoxysilyl group which (F) silane compound has is converted into a silanol group by hydrolysis, and this silanol group can form a covalent bond with a hydroxy group on the underlying substrate surface.
  • Examples of (F) silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, and N- (2-aminoethyl).
  • the content of the (F) silane compound in the photosensitive resin composition of the present invention is 0.1 to 10 wt. Part is preferable, and 0.5 to 7 parts by weight is more preferable.
  • content of a silane compound is less than 0.1 weight part, the effect of an adhesive improvement or chemical-resistance improvement may be inadequate. On the other hand, if it exceeds 10 parts by weight, it may cause a residue after development, and the storage stability of the coating liquid may decrease.
  • the photosensitive resin composition of the present invention preferably further contains (G) a maleimide compound.
  • a maleimide compound a general maleimide or a maleimide derivative can be used.
  • the photosensitive resin composition contains (G) maleimide compound, thereby improving the chemical resistance, vacuum resistance, moisture heat resistance and artificial sweat resistance of the resulting cured film without impairing the storage stability of the coating liquid. Can do.
  • the structure derived from maleimide in the maleimide compound contributes to the stabilization of the photosensitive resin composition, and suppresses the progress of the reaction during storage of the coating liquid, thereby suppressing deterioration in chemical resistance or adhesion. Presumed to be.
  • the maleimide compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the chemical resistance, vacuum resistance, heat and humidity resistance, artificial sweat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity and chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton.
  • maleimide compounds For example, Maleimide, N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, Nn-hexylmaleimide, N-dodecylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N- (2, 4-dimethylcyclohexyl) maleimide, N-vinylmaleimide, N- (meth) acrylic maleimide, N-methoxymethylmaleimide, N- (2-ethoxyethyl) maleimide, N- (4-butoxyethyl) maleimide, N-[(meth) acryloxymethyl] maleimide, N- [2- (meth) acryloxyethyl] maleimide, N- [3- (meth) acryloxypropyl] maleimide
  • the maleimide compound is more preferably a bismaleimide compound represented by any one of the general formulas (3) to (5).
  • the bismaleimide compound is a compound having two maleimide-derived structures, and has two sites each incorporated as part of a three-dimensional network structure and two sites capable of coordination on the underlying substrate surface. For this reason, it is considered that the crosslink density and the adhesion to the underlying substrate surface are further improved, and the chemical resistance, vacuum resistance, moist heat resistance and artificial sweat resistance of the resulting cured film can be further improved.
  • the bismaleimide compound preferably has an aromatic cyclic skeleton or an aliphatic cyclic skeleton. It is considered that the chemical resistance, vacuum resistance, heat and humidity resistance, artificial sweat resistance and heat resistance of the obtained cured film are further improved by the hydrophobicity and chemical stability of the aromatic cyclic skeleton or the aliphatic cyclic skeleton.
  • X represents an alkylene chain having 1 to 10 carbon atoms or an arylene chain having 6 to 15 carbon atoms.
  • R 5 to R 10 are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom. Represents an alkoxy group or a hydroxy group of ⁇ 6, and l, m, n and o each independently represents an integer of 1 to 4)
  • X is preferably an alkylene chain having 1 to 6 carbon atoms or an arylene chain having 6 to 10 carbon atoms, and R 5 to R 10 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 1 to 4 alkoxy groups or hydroxy groups are preferred.
  • the alkylene chain, arylene chain, alkyl group and alkoxy group may be either unsubstituted or substituted.
  • the bismaleimide compound examples include 1,2-bis (maleimido) ethane, 1,3-bis (maleimido) propane, 1,4-bis (maleimido) butane, 1,5-bis (maleimido) pentane, 6-bis (maleimido) hexane, 2,2,4-trimethyl-1,6-bis (maleimido) hexane, N, N′-1,3-phenylenebis (maleimide), 4-methyl-N, N′- 1,3-phenylenebis (maleimide), N, N′-1,4-phenylenebis (maleimide), 3-methyl-N, N′-1,4-phenylenebis (maleimide), 4,4′-bis (Maleimido) diphenylmethane, 3,3′-diethyl-5,5′-dimethyl-4,4′-bis (maleimido) diphenylmethane or 2,2-bis [4- (4-maleimidophenol) P) propane], and 4,4′-bis (
  • the content of the (G) maleimide compound in the photosensitive resin composition of the present invention is 0.1 to 20 weights when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. Part is preferable, and 1 to 15 parts by weight is more preferable.
  • the maleimide compound is less than 0.1 parts by weight, the chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance improvement effect may be insufficient. On the other hand, if it exceeds 20 parts by weight, it may cause a residue after development.
  • the photosensitive resin composition of the present invention preferably further contains (B2) a radical polymerizable compound having a fluorene skeleton.
  • the radically polymerizable compound having a fluorene skeleton refers to a compound having a fluorene skeleton and a plurality of ethylenically unsaturated double bond groups in the molecule.
  • Examples of the radically polymerizable compound having a fluorene skeleton include a compound represented by the general formula (6), and the like, but a radically polymerizable compound having a (meth) acrylic group that facilitates radical polymerization. Is preferred.
  • (C) radical generated from the photopolymerization initiator causes (B2) polymerization of the radical polymerizable compound having a fluorene skeleton to progress, and the exposed portion of the photosensitive resin composition is insolubilized in the aqueous alkali solution.
  • (B2) By containing the radically polymerizable compound which has a fluorene skeleton, the chemical resistance of the obtained cured film, vacuum resistance, heat-and-moisture resistance, artificial sweat resistance, and heat resistance can be improved.
  • the double bond equivalent of the radically polymerizable compound having a fluorene skeleton is preferably 200 to 500 g / mol from the viewpoints of sensitivity during exposure and hardness of the cured film.
  • X represents a direct bond or oxygen.
  • Y also represents a direct bond.
  • X oxygen
  • Y represents an alkylene chain having 1 to 10 carbon atoms.
  • R 11 and R 12 are Each independently represents an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms
  • each of R 13 to R 16 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, Represents an alkoxy group having 1 to 6 carbon atoms or a hydroxy group.
  • Y is preferably an alkylene chain having 1 to 6 carbon atoms.
  • R 11 and R 12 are preferably each independently an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms.
  • R 13 to R 16 are preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group.
  • the alkylene chain, alkenyl group, alkenyloxy group, alkyl group and alkoxy group may be either unsubstituted or substituted.
  • fluorene skeleton-containing radical polymerizable compound examples include Ogsol (registered trademark) EA-50P, EA-0200, EA-0250P, EA-500, EA-1000, EA-F5003, EA-F5503 or EA-F5510 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), 9,9-bis [4- (2- (meth) acryloxyethoxy) phenyl] fluorene, 9,9-bis [ 4- (3- (meth) acryloxypropoxy) phenyl] fluorene, 9,9-bis [4- (2- (meth) acryloxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2- (meth) acryloxyethoxy) -3,5-dimethylphenyl] fluorene or 9,9-bis (4- (meth) acryloxyphenyl) Fluorene, and the like.
  • Ogsol registered trademark
  • the content of the (B2) radical polymerizable compound having a fluorene skeleton in the photosensitive resin composition of the present invention is (A) when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight.
  • the amount is preferably 0.1 to 20 parts by weight, and more preferably 1 to 10 parts by weight.
  • the radically polymerizable compound having a fluorene skeleton is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance, or heat resistance may be insufficient.
  • the amount is more than 20 parts by weight, it may cause a residue after development or a decrease in the hardness of the cured film.
  • the photosensitive resin composition of the present invention preferably further contains (B3) a radical polymerizable compound having a carboxy group.
  • the radical polymerizable compound having a carboxy group refers to a compound having a carboxy group and a plurality of ethylenically unsaturated double bond groups in the molecule.
  • Examples of the radically polymerizable compound having a carboxy group include a compound represented by the general formula (7) or (8), and the like. A radically polymerizable compound is preferred.
  • (C) radicals generated from the photopolymerization initiator cause (B3) polymerization of the radical polymerizable compound having a carboxy group to progress, and the exposed portion of the photosensitive resin composition is insolubilized in the aqueous alkali solution. A pattern can be formed.
  • (B3) By containing the radically polymerizable compound which has a carboxy group, the residue generation
  • the carboxy group contained in the radically polymerizable compound having a carboxy group improves the solubility in an alkaline developer, so that it is presumed that generation of a residue after development is suppressed.
  • the double bond equivalent of the radical polymerizable compound is preferably 80 to 400 g / mol from the viewpoints of sensitivity during exposure and hardness of the cured film.
  • R 17 to R 24 each independently represents an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms.
  • X represents an alkylene chain having 1 to 6 carbon atoms, an alkylene chain having 2 to 8 carbon atoms having one ethylenically unsaturated double bond, a cycloalkylene chain having 4 to 7 carbon atoms, or an arylene chain having 6 to 10 carbon atoms.
  • R 17 to R 24 are preferably each independently an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms.
  • the alkylene chain, cycloalkylene chain, arylene chain, alkenyl group and alkenyloxy group may be either unsubstituted or substituted.
  • a carboxy group-containing radical polymerizable compound includes a hydroxy group-containing unsaturated compound having a hydroxy group and a plurality of ethylenically unsaturated double bond groups in the molecule, and a compound having an acid anhydride group in the molecule; It is obtained by reacting.
  • Examples of the hydroxy group-containing unsaturated compound having one or more hydroxy groups and a plurality of ethylenically unsaturated double bond groups in the molecule include trimethylolpropane di (meth) acrylate and ditrimethylolpropane di (meth) acrylate.
  • Examples of the compound having an acid anhydride group in the molecule include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride, with succinic anhydride being preferred.
  • radical polymerizable compound having a carboxy group examples include Aronix (registered trademark) M-510 and M-520 (both are manufactured by Toagosei Co., Ltd.), succinic acid mono [2,2, 2-tris ((meth) acryloxymethyl) ethyl] or succinic acid mono [2,2-bis ((meth) acryloxymethyl) -3- [2,2,2-tris ((meth) acryloxymethyl) Ethyloxy] propyl].
  • the content of the radically polymerizable compound (B3) having a carboxy group in the photosensitive resin composition of the present invention is as follows when the total of (A) the acrylic resin and (B) the radically polymerizable compound is 100 parts by weight:
  • the amount is preferably 1 to 40 parts by weight, and more preferably 5 to 30 parts by weight.
  • (B3) When the amount of the radical polymerizable compound having a carboxy group is less than 1 part by weight, the effect of suppressing the residue after development may be insufficient. On the other hand, if it exceeds 40 parts by weight, it may cause a decrease in the hardness of the cured film and a decrease in chemical resistance.
  • the photosensitive resin composition of the present invention preferably further contains (H) a fluorene compound.
  • (H) fluorene compounds include compounds represented by any one of the general formulas (9) to (12).
  • (H) By containing a fluorene compound the chemical resistance, vacuum resistance, heat-and-moisture resistance, artificial sweat resistance, and heat resistance of the cured film obtained can be improved.
  • the fluorene compound is taken in as a part of a three-dimensional network structure by reacting with a resin or the like by heat.
  • X represents a direct bond or oxygen.
  • Y also represents a direct bond.
  • X oxygen
  • Y represents an alkylene chain having 1 to 10 carbon atoms.
  • R 25 and R 26 Each independently represents a glycidoxy group, a hydroxy group or an amino group, each of R 27 to R 30 independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or Represents a hydroxy group.
  • Y is preferably an alkylene chain having 1 to 6 carbon atoms.
  • R 25 to R 30 are preferably each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group.
  • the alkylene chain, alkyl group, and alkoxy group may be either unsubstituted or substituted.
  • Examples of (H) fluorene compounds include Ogsol (registered trademark) PG, PG-100, EG, EG-200, EG-210 (all of which are manufactured by Osaka Gas Chemical Co., Ltd.), oncoat (Registered trademark) EX-1010, EX-1011, EX-1012, EX-1020, EX-1020, EX-1030, EX-1040, EX-1050, EX-1051, EX-1020M80 or EX -1020M70 (all of which are manufactured by Nagase ChemteX Corporation), 9,9-bis [4- (2-glycidoxyethoxy) phenyl] fluorene, 9,9-bis [4- (3-glycidoxy Propoxy) phenyl] fluorene, 9,9-bis [4- (2-glycidoxyethoxy) -3-methylphenyl] fluorene, 9,9-bis [4- (2 Glycidoxyethoxy) -3,5-dimethylphenyl]
  • Ogsol registered trademark
  • PG PG-100, EG, EG-200, EG-210 or EG-250 from the viewpoint of improving chemical resistance, vacuum resistance, heat and moisture resistance and artificial sweat resistance of the film.
  • ONCOAT registered trademark
  • EX-1010, EX-1011, EX-1012, EX-1020, EX-1030, EX-1030, EX-1040, EX-1050, EX-1051, EX-1020M80 or EX-1020M70 all of which are manufactured by Nagase ChemteX Corp.
  • the content of (H) fluorene compound in the photosensitive resin composition of the present invention is 1 to 30 parts by weight when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. Preferably, 5 to 25 parts by weight are more preferable.
  • the amount of (H) fluorene compound is less than 1 part by weight, the effects of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance may be insufficient.
  • it is more than 30 parts by weight it may cause a residue after development, and the storage stability of the coating liquid may be lowered.
  • the photosensitive resin composition of the present invention preferably further contains (I) a polyfunctional epoxy compound.
  • a polyfunctional epoxy compound examples include compounds represented by any one of the general formulas (13) to (18).
  • a polyfunctional epoxy compound By containing a polyfunctional epoxy compound, chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance and heat resistance of the obtained cured film can be improved.
  • the epoxy site of the polyfunctional epoxy compound is taken in as a part of the three-dimensional network structure by reacting with a resin or the like by heat.
  • R 31 to R 40 and R 43 to R 48 each independently represent hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxy group.
  • R 41 , R 42 and R 49 each independently represents hydrogen, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • R 31 to R 40 and R 43 to R 48 are preferably each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a hydroxy group.
  • R 41 , R 42 and R 49 are preferably each independently hydrogen, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • the alkyl group, alkoxy group and aryl group may be either unsubstituted or substituted.
  • Examples of (I) polyfunctional epoxy compounds include 1,1-bis (4-glycidoxyphenyl) -1- [4- [1- (4-glycidoxyphenyl) -1-methylethyl] phenyl]. Ethane, 2,2-bis (4-glycidoxyphenyl) propane, 1,1-bis (4-glycidoxyphenyl) -1-phenylethane, 1,1,1-tris (4-glycidoxyphenyl) ) Methane, 1,1,1-tris (4-glycidoxyphenyl) ethane, 1,1-bis (4-glycidoxyphenyl) -1- (1-naphthyl) ethane, 1,1-bis (4 -Glycidoxyphenyl) -1- (2-naphthyl) ethane, 1,1-bis (4-glycidoxy-1-naphthyl) -1- (4-glycidoxyphenyl) ethane, 1,1-bis (5 -Gly
  • the content of the (I) polyfunctional epoxy compound in the photosensitive resin composition of the present invention is 1 to 30 weights when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. Part is preferable, and 5 to 25 parts by weight is more preferable.
  • the polyfunctional epoxy compound is less than 1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance, artificial sweat resistance or heat resistance may be insufficient. On the other hand, if it is more than 30 parts by weight, it may cause a residue after development, and the storage stability of the coating liquid may be lowered.
  • the photosensitive resin composition of the present invention may further contain an isocyanate compound.
  • the isocyanate compound here includes a blocked isocyanate compound in which an isocyanate group is blocked.
  • chemical resistance, vacuum resistance, wet heat resistance, and artificial sweat resistance of the obtained cured film can be improved.
  • the isocyanate group is a site capable of reacting with a carboxy group or the like in the resin by heat, it is presumed that the isocyanate compound functions as a crosslinking agent.
  • an isocyanate compound functions as a crosslinking agent, the film density of a cured film increases, and it is estimated that the chemical resistance, vacuum resistance, heat-and-moisture resistance, and artificial sweat resistance of the obtained cured film improve.
  • isocyanate compound examples include hexamethylene diisocyanate, isophorone diisocyanate, tolylene-2,6-diisocyanate, methylenediphenyl-4,4′-diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, and 1,3-bis (isocyanate methyl).
  • tris (6-isocyanatohexyl) isocyanuric acid tris (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl) isocyanuric acid or 1,3,5 -Tris (6-isocyanatohexyl) biuret is preferred.
  • the content of the isocyanate compound in the photosensitive resin composition of the present invention is preferably 0.1 to 10 parts by weight when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. 0.5 to 7 parts by weight is more preferable. If the isocyanate compound is less than 0.1 parts by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance or artificial sweat resistance may be insufficient. On the other hand, if it is more than 10 parts by weight, it may cause a residue after development, and the storage stability of the coating liquid may be lowered.
  • the photosensitive resin composition of the present invention may further contain a urea compound having an ethylenically unsaturated double bond group.
  • a urea compound having an ethylenically unsaturated double bond group By containing a urea compound having an ethylenically unsaturated double bond group, the chemical resistance, vacuum resistance, moist heat resistance and artificial sweat resistance of the resulting cured film can be improved.
  • the urea site is presumed to function as a site capable of reacting with a resin or the like by heat and capable of coordinating with the underlying substrate surface.
  • a crosslinked structure can be formed by radical polymerization with an ethylenically unsaturated double bond group bonded to a resin or the like.
  • the urea compound having an ethylenically unsaturated double bond group functions as a cross-linking agent, so that the film density of the cured film increases, and the resulting cured film has chemical resistance, vacuum resistance, heat and humidity resistance, and artificial sweat resistance. Presumed to improve.
  • urea compounds having an ethylenically unsaturated double bond group include 1-allylurea, 1-vinylurea, 1-allyl-2-thiourea, 1-vinyl-2-thiourea, 1-allyl-3. -Methyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea or 1-methyl-3- (4-vinylphenyl) -2-thiourea.
  • the content of the urea compound having an ethylenically unsaturated double bond group in the photosensitive resin composition of the present invention is as follows when the total of (A) acrylic resin and (B) radical polymerizable compound is 100 parts by weight. 0.1 to 10 parts by weight is preferable, and 0.5 to 7 parts by weight is more preferable. If the urea compound having an ethylenically unsaturated double bond group is less than 0.1 part by weight, the effect of improving chemical resistance, vacuum resistance, moist heat resistance or artificial sweat resistance may be insufficient. On the other hand, if it is more than 10 parts by weight, it may cause a residue after development, and the storage stability of the coating liquid may be lowered.
  • the photosensitive resin composition of the present invention may further contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a suitable amount of a polymerization inhibitor, generation of residues after development can be suppressed and high resolution can be ensured. It is presumed that the polymerization inhibitor can capture excessive radicals generated from the photopolymerization initiator (C) by light irradiation during exposure, and the progress of excessive radical polymerization can be suppressed.
  • polymerization inhibitor examples include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone, and t-butylcatechol.
  • polymerization inhibitors examples include IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565 or 295 (all of which are manufactured by BASF).
  • the photosensitive resin composition of the present invention may further contain an ultraviolet absorber.
  • an ultraviolet absorber By containing an appropriate amount of the ultraviolet absorber, generation of residues after development can be suppressed, high resolution can be ensured, and light resistance of the resulting cured film is improved. This is presumed to be because the ultraviolet absorbent captures scattered light, reflected light, and the like, which are generated during light irradiation during exposure, and the progress of excessive radical polymerization can be suppressed. Moreover, also in the cured film obtained, it is estimated that light resistance improves because an ultraviolet absorber captures the irradiated light.
  • a benzotriazole compound As the ultraviolet absorber, a benzotriazole compound, a benzophenone compound, a triazine compound, or the like is preferable from the viewpoint of transparency and non-colorability.
  • benzotriazole compound examples include 2- (2′-hydroxyphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) -2H-benzotriazole, 2- (2′-hydroxy -5′-t-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -2H-benzotriazole, 2- [2′-hydroxy- 3 ′, 4′-bis (1-methyl-1-phenylethyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-pentylphenyl) -2H-benzo Triazole, 2- (2′-hydroxy-5′-t-octylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-3′-dodecyl) -5'-methylphenyl) -2H-benzotriazole, 2- [2'-
  • benzophenone compound examples include 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4-octyloxybenzophenone.
  • triazine compound examples include 2- (2′-hydroxy-4′-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- [2′-hydroxy-4 ′-(2 -Hydroxy-3-dodecyloxypropoxy) phenyl] -4,6-bis (2 ', 4'-dimethylphenyl) -1,3,5-triazine, 2- [2'-hydroxy-4'-[2- Hydroxy-3- (2-ethylhexyloxy) propoxy] phenyl] -4,6-bis (2 ′, 4′-dimethylphenyl) -1,3,5-triazine or 2,4-bis (2′-hydroxy- And 4'-butoxyphenyl) -6- (2 ', 4'-dibutoxy) -1,3,5-triazine.
  • the photosensitive resin composition of the present invention may further contain a surfactant.
  • a surfactant By containing an appropriate amount of the surfactant, leveling properties at the time of coating can be improved, the occurrence of coating unevenness can be suppressed, and a uniform coating film can be obtained.
  • surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, a polyalkylene oxide-based surfactant, and a poly (meth) acrylate-based surfactant.
  • fluorine-based surfactant examples include 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctyl hexyl ether, Octaethylene glycol bis (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis (1,1, 2,2-tetrafluorobutyl) ether, hexapropylene glycol bis (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8, 8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodeca N- [3- (perfluorooctanesulfonamid
  • compounds having a fluoroalkyl group or a fluoroalkylene chain at any of the terminal, main chain, and side chain such as monoperfluoroalkylethyl phosphate, can be mentioned.
  • Examples of such compounds include MegaFac (registered trademark) F-142D, F-172, F-173, F-183, F-444, F-445, F-470, and F-470.
  • F-475, F-477, F-555, or F-559 "(all of which are manufactured by Dainippon Ink & Chemicals, Inc.), Ftop (registered trademark) EF301, 303 or 352 (and above) , All manufactured by Mitsubishi Materials Electronic Chemical Co., Ltd.), Florard (registered trademark) FC-430 or FC-431 (all of which are manufactured by Sumitomo 3M), Asahi Guard (registered trademark) AG710 ”(Asahi Glass ( Manufactured by the same company), Surflon (registered trademark) S-382, “SC-101, SC-102, SC-103, SC-104, SC-105, or SC-106 (above, This is also manufactured by AGC Seimi Chemical Co., Ltd.), BM-1000 or BM-1100 (both manufactured by Yusho Co., Ltd.), or NBX-15, FTX-218 or DFX-218 (all manufactured by Co., Ltd.) Neos).
  • silicone surfactant examples include SH28PA, SH7PA, SH21PA, SH30PA or ST94PA (all of which are manufactured by Toray Dow Corning Co., Ltd.) or BYK-301, BYK-307, BYK-331, BYK-333. Another example is BYK-345 (all of which are manufactured by Big Chemie Japan Co., Ltd.).
  • the content of the surfactant in the photosensitive resin composition of the present invention is generally preferably 0.0001 to 1% by weight of the entire photosensitive resin composition, and is preferable.
  • the photosensitive resin composition of the present invention may further contain various curing agents that promote thermal curing of the resin composition.
  • the curing agent include nitrogen-containing organic compounds, silicone resin curing agents, metal alkoxides, methylol group-containing melamine derivatives, and methylol group-containing urea derivatives.
  • the photosensitive resin composition of the present invention preferably has negative photosensitivity.
  • negative photosensitivity coloring during thermosetting can be suppressed, and a cured film with higher transparency can be obtained.
  • a crosslinking reaction can easily proceed during UV curing, and a cured film having better hardness, moisture and heat resistance, artificial sweat resistance, adhesion, chemical resistance, and vacuum resistance can be obtained. It becomes possible.
  • a typical production method of the photosensitive resin composition of the present invention will be described.
  • the (F) silane compound is added to an arbitrary (E) solvent and stirred.
  • (I) polyfunctional epoxy compound and other additives are added and dissolved by stirring.
  • B) a radical polymerizable compound, (B2) a fluorene skeleton-containing radical polymerizable compound and (B3) a carboxy group-containing radical polymerizable compound are added, and the mixture is stirred for 20 minutes to 3 hours. Make a solution. Then, the photosensitive resin composition of this invention is obtained by filtering the obtained solution.
  • the photosensitive resin composition of the present invention is applied on a substrate.
  • a substrate for example, a substrate in which a metal oxide such as ITO, a metal such as molybdenum, silver, copper, or aluminum, or CNT (Carbon Nano Tube) is formed on a glass as an electrode or a wiring is used.
  • the application method include micro gravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.
  • the coating film thickness varies depending on the coating method, solid content concentration and viscosity of the photosensitive resin composition, but is usually applied so that the film thickness after coating and pre-baking is 0.1 to 15 ⁇ m.
  • the substrate coated with the photosensitive resin composition is prebaked to prepare a prebaked film of the photosensitive resin composition.
  • Prebaking is preferably performed at 50 to 150 ° C. for 30 seconds to several hours using an oven, a hot plate, or infrared rays. If necessary, after pre-baking at 80 ° C. for 2 minutes, pre-baking at 120 ° C. for 2 minutes may be used for pre-baking in two or more stages.
  • exposure is performed using an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA).
  • an exposure machine such as a stepper, mirror projection mask aligner (MPA), or parallel light mask aligner (PLA).
  • MPA mirror projection mask aligner
  • PPA parallel light mask aligner
  • the active actinic radiation to be irradiated at the time of exposure ultraviolet rays, visible rays, electron beams, X-rays, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser or the like can be used, but mercury lamp j-ray (wavelength 313 nm). I-line (wavelength 365 nm), h-line (wavelength 405 nm) or g-line (wavelength 436 nm) is preferably used.
  • the exposure amount is usually about 10 to 4000 J / m 2 (i-line illuminometer value), and exposure can be performed through a mask having
  • baking before development may be performed.
  • pre-development baking it is possible to expect effects such as improvement in resolution during development and increase in the allowable range of development conditions.
  • the baking temperature is preferably 50 to 180 ° C, more preferably 60 to 150 ° C.
  • the baking time is preferably 10 seconds to several hours.
  • the exposed film is developed for an arbitrary time using an automatic developing device or the like, so that the unexposed portion is removed with a developer and a relief pattern is obtained.
  • a known alkali developer is generally used.
  • the developer include organic alkaline developer or ammonia, tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine.
  • An aqueous solution of an alkaline compound such as dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylene diamine or hexamethylene diamine is mentioned. preferable.
  • the same alcohols, ketones, ethers, N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N as the solvent (E) contained in the photosensitive resin composition -Dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphortriamide or ⁇ -butyrolactone may be used.
  • solvents methanol, ethanol, isopropyl alcohol, water, methyl carbitol, ethyl carbitol, toluene, xylene, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate,
  • a mixed solution in combination with a poor solvent for the photosensitive resin composition such as ethyl-3-ethoxypropionate, 2-heptanone, cyclopentanone, cyclohexanone, or ethyl acetate may be used.
  • the above-described developer is directly applied to the exposed film, the developer is sprayed and emitted, the exposed film is immersed in the developer, and the exposed film is exposed. It can be performed by a method such as applying ultrasonic waves while being immersed in the developer.
  • the exposed film is preferably brought into contact with the developer for 5 seconds to 10 minutes.
  • rinsing treatment may be performed by adding alcohols such as ethanol or isopropyl alcohol, esters such as propylene glycol monomethyl ether acetate, or acids such as carbon dioxide, hydrochloric acid or acetic acid to water.
  • Methanol, ethanol, isopropyl alcohol, ethyl lactate, ethyl pyruvate, propylene glycol monomethyl ether acetate, methyl-3-methoxypropionate, ethyl-3- Ethoxypropionate, 2-heptanone or ethyl acetate is preferred.
  • middle baking may be performed as necessary. By performing middle baking, effects such as improvement in resolution after thermosetting and control of the pattern shape after thermosetting can be expected.
  • Middle baking uses an oven, a hot plate, infrared rays, or the like, and the baking temperature is preferably 60 to 250 ° C, more preferably 70 to 220 ° C.
  • the baking time is preferably 10 seconds to several hours.
  • a cured film of the photosensitive resin composition of the present invention is obtained by heating at a temperature of 120 to 280 ° C. for 10 minutes to several hours.
  • This heat treatment can be performed in an air atmosphere or an inert gas atmosphere such as nitrogen.
  • this heat treatment may be performed stepwise, or may be performed continuously for 5 minutes to 5 hours.
  • the thickness of the cured film obtained by thermosetting the photosensitive resin composition of the present invention is preferably 0.1 to 15 ⁇ m. Further, it is preferable that the hardness is 4H or more and the transmittance is 90% or more at a film thickness of 1.5 ⁇ m.
  • permeability here means the transmittance
  • the cured film obtained by thermosetting the photosensitive resin composition of the present invention includes various types such as a protective film for a touch panel, various hard coat materials, a flattening film for TFT, an overcoat for a color filter, an antireflection film, or a passivation film. It can be used for various insulating films such as protective films, optical filters, touch panel insulating films, TFT insulating films, or color filter photo spacers. Among these, since it has high hardness, transparency, chemical resistance, vacuum resistance, and heat resistance, it can be suitably used as a protective film for touch panels or an insulating film for touch panels. Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. In particular, since a particularly high hardness is required for a capacitive touch panel, the cured film of the present invention can be used particularly suitably.
  • the cured film obtained by thermosetting the photosensitive resin composition of the present invention has high moisture resistance and artificial sweat resistance, it can be suitably used as a metal wiring protective film.
  • a metal wiring protective film By forming the cured film of the present invention on the metal wiring, deterioration due to metal corrosion or the like (conductivity, decrease in resistance value, etc.) can be prevented.
  • the metal wiring to be protected include one or more selected from the group consisting of molybdenum, silver, copper, aluminum, chromium, titanium, ITO, IZO (Indium Zinc Oxide), AZO (Aluminum Zinc Oxide), ZnO 2 and CNT.
  • the metal wiring to contain is mentioned.
  • the cured film obtained by thermosetting the photosensitive resin composition of the present invention is a protective film or insulating film for metal wiring containing at least one selected from the group consisting of molybdenum, silver, copper, aluminum and CNT. Preferably used.
  • the acrylic resin had a weight average molecular weight (Mw) of 11,000, an acid value of 100, and a double bond equivalent of 730.
  • Synthesis Example 2 Synthesis of acrylic resin solution (A-2) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 26.15 g of PGMEA, and 13.44 g (15 mol) of N-cyclohexylmaleimide %), 19.37 g (45 mol%) of methacrylic acid, 20.02 g (40 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, Using 0.186 g (0.3 mol%) of 4-methoxyphenol and 53.10 g of PGMEA, polymerization was performed in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-2). PGMEA was added to the obtained acrylic resin solution (A-2) so that the solid concentration was 35% by weight.
  • the weight average molecular weight (Mw) of the acrylic resin was 15,000, the acid value was 109,
  • Synthesis Example 5 Synthesis of acrylic resin solution (A-5) 2,21'-azobis (isobutyronitrile) 0.821 g (1 mol%), PGMEA 35.14 g, N-cyclohexylmaleimide 53.77 g (60 mol) %), 17.22 g (40 mol%) of methacrylic acid, 10.66 g (15 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, and 0.186 g (0.3 mol of 4-methoxyphenol) %) And 71.34 g of PGMEA was used for polymerization in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-5). PGMEA was added to the obtained acrylic resin solution (A-5) so that the solid content concentration was 35% by weight. The weight average molecular weight (Mw) of the acrylic resin was 12,000, the acid value was 86, and the double bond equivalent was 1090.
  • Mw weight average molecular
  • Synthesis Example 6 Synthesis of acrylic resin solution (A-6) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 28.35 g of PGMEA, and 25.38 g (30 mol) of N-phenylmaleimide %), 19.37 g (45 mol%) of methacrylic acid, 12.52 g (25 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, Using 0.186 g (0.3 mol%) of 4-methoxyphenol and 57.55 g of PGMEA, polymerization was carried out in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-6). PGMEA was added to the obtained acrylic resin solution (A-6) so that the solid content concentration was 35% by weight. The weight average molecular weight (Mw) of the acrylic resin was 12,000, the acid value was 105, and the
  • Synthesis Example 7 Synthesis of acrylic resin solution (A-7) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 29.39 g of PGMEA, and 27.49 g (30 mol) of N-benzylmaleimide %), 19.37 g (45 mol%) of methacrylic acid, 12.52 g (25 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, Polymerization was carried out in the same manner as in Synthesis Example 1 using 0.186 g (0.3 mol%) of 4-methoxyphenol and 59.67 g of PGMEA to obtain an acrylic resin solution (A-7).
  • PGMEA was added to the resulting acrylic resin solution (A-7) so that the solid content concentration was 35% by weight.
  • the weight average molecular weight (Mw) of the acrylic resin was 11,000, the acid value was 98, and the double bond equivalent was 740.
  • Synthesis Example 8 Synthesis of acrylic resin solution (A-8) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 25.97 g of PGMEA, and N- (2-hydroxyethyl) maleimide 20.58 g (30 mol%), 19.37 g (45 mol%) of methacrylic acid, 12.52 g (25 mol%) of methyl methacrylate, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g of dimethylbenzylamine (1 mol%), 0.186 g (0.3 mol%) of 4-methoxyphenol and 52.72 g of PGMEA were used for polymerization in the same manner as in Synthesis Example 1 to obtain an acrylic resin solution (A-8).
  • PGMEA was added to the obtained acrylic resin solution (A-8) so that the solid content concentration was 35% by weight.
  • the weight average molecular weight (Mw) of the acrylic resin was 13,000, the acid value was 103, and the double bond equivalent was 670.
  • Synthesis Example 12 Synthesis of acrylic resin solution (A-12) 0.821 g (1 mol%) of 2,2′-azobis (isobutyronitrile), 23.34 g of PGMEA, and 21.52 g (50 mol%) of methacrylic acid 10.01 g (20 mol%) of methyl methacrylate, 15.62 g (30 mol%) of styrene, 14.22 g (20 mol%) of glycidyl methacrylate, 0.676 g (1 mol%) of dimethylbenzylamine, 4-methoxy Using 0.186 g (0.3 mol%) of phenol and 47.39 g of PGMEA, polymerization was carried out in the same manner as in Synthesis Example 10 to obtain an acrylic resin solution (A-12). PGMEA was added to the obtained acrylic resin solution (A-12) so that the solid content concentration was 35% by weight.
  • the weight average molecular weight (Mw) of the acrylic resin was 20,000, the acid value was 113, and the double bond equivalent was
  • Example 1 The evaluation method in Example 1 is shown below.
  • Tempax glass substrate manufactured by AGC Techno Glass Co., Ltd.
  • glass substrate on which a single layer Cr film was formed by sputtering single layer Cr film-formed substrate; manufactured by Kuramoto Seisakusho; hereinafter referred to as “Cr substrate” Used without treatment.
  • Sensitivity A post-development film of the photosensitive resin composition was produced on the Cr substrate by the method described in Example 1 below. After development, the resolution pattern is observed using an FPD inspection microscope (MX-61L; manufactured by Olympus Corporation), and the exposure amount (i-line illuminometer value, which forms a 30 ⁇ m L & S pattern in a 1: 1 width) Hereinafter, “optimum exposure amount”) was defined as sensitivity.
  • Transmittance A cured film of the photosensitive resin composition was produced on the Tempax glass substrate by the method described in Example 1 below. First, only the Tempax glass substrate was measured using an ultraviolet-visible spectrophotometer (MultiSpec-1500; manufactured by Shimadzu Corporation), and the ultraviolet-visible absorption spectrum was used as a reference. Next, the produced cured film was measured with a single beam, the transmittance per 1.5 ⁇ m at a wavelength of 400 nm was determined, and the transmittance was calculated from the difference from the reference.
  • MultiSpec-1500 ultraviolet-visible spectrophotometer
  • Pencil Hardness A cured film of the photosensitive resin composition was produced on the Cr substrate by the method described in Example 1 below. Using a manual pencil scratch hardness tester (850-56; manufactured by Coating Tester Co., Ltd.), the pencil hardness of the prepared cured film was measured based on “JIS K5600-5-4 (1999)”.
  • a cured film of the photosensitive resin composition was produced on the ITO substrate by the method described in Example 1 below.
  • the produced cured film was depressurized using a sputtering apparatus (HSR-521A; manufactured by Shimadzu Corporation) while being heated to 100 ° C. until reaching a pressure of 7.0 to 7.5 ⁇ 10 ⁇ 4 , Exposed under high vacuum.
  • HSR-521A sputtering apparatus
  • the cured film exposed to high vacuum is immersed in water at 40 ° C. while irradiating it with 39 kHz and 100 W ultrasonic waves using a tabletop ultrasonic cleaner (UT-104; manufactured by Sharp Corporation). Soaked for 20 minutes.
  • UT-104 tabletop ultrasonic cleaner
  • a +: Discolored area of MAM surface 0% and no change in appearance of cured film surface
  • the area where the artificial sweat solution was dropped on the MAM substrate was visually evaluated for the area on which the MAM surface was corroded and the appearance change of the cured film surface. Judgment was made as follows according to the corrosion area of the MAM surface and the appearance change of the surface of the cured film, and A +, A, and B were set as acceptable.
  • Corrosion area of MAM surface 0%, no change in appearance of cured film surface
  • E Corrosion area of MAM surface 65 to 100% There is discoloration on the surface of the cured film.
  • a part of the photosensitive resin composition prepared by the method described in Example 1 was left at 23 ° C. for 7 days. After the elapse of 7 days, a cured film of the photosensitive resin composition was prepared on the MAM substrate by the method described in Example 1 below after being left at 23 ° C. for 7 days. The prepared cured film was measured for adhesion of the cured film to the substrate based on “JIS K5600-5-6 (1999)” in the same manner as in (10) above.
  • Example 1 Under a yellow light, 1.282 g of PGMEA, 6.375 g of MB, and 8.500 g of EDM were weighed, and 0.0693 g of KBM-903 was added and stirred. Next, 0.173 g of OXE-01, 0.0347 g of ZC-150, and 0.150 g of a 5 wt% PGMEA solution of BYK-333 were added and dissolved by stirring. Next, 4.950 g of the acrylic resin solution (A-1) obtained in Synthesis Example 1 (35 wt% PGMEA solution) and 3.465 g of 50 wt% PGMEA solution of DPHA were added and stirred to obtain a uniform solution. It was. Then, the obtained solution was filtered with a 0.2 ⁇ m filter to prepare a negative photosensitive resin composition 1.
  • the prepared photosensitive resin composition 1 was applied on a substrate by spin coating at an arbitrary rotation number using a spin coater (MS-A100; manufactured by Mikasa Co., Ltd.), and then hot plate (SCW-636; Dainippon). Prebaked at 100 ° C. for 3 minutes using Screen Manufacturing Co., Ltd. to prepare a prebaked film having a thickness of about 2.0 ⁇ m.
  • MS-A100 manufactured by Mikasa Co., Ltd.
  • SCW-636 hot plate
  • Pattern exposure was performed with j-line (wavelength 313 nm), i-line (wavelength 365 nm), h-line (wavelength 405 nm) and g-line (wavelength 436 nm) of an ultra-high pressure mercury lamp.
  • Example 50 A touch panel member was produced according to the following procedure.
  • a film thickness of 150 nm is obtained by sputtering a glass substrate having a thickness of about 1 mm for 12.5 minutes using a sputtering apparatus at an RF power of 1.4 kW and a degree of vacuum of 6.65 ⁇ 10 ⁇ 1 Pa. Then, an ITO film having a surface resistance of 15 ⁇ / ⁇ was formed. Next, a positive photoresist OFPR-800 was applied onto ITO by spin coating at an arbitrary rotation number using a spin coater, and then pre-baked at 80 ° C. for 20 minutes using a hot plate to obtain a film thickness of 1.1 ⁇ m. A resist film was obtained.
  • the cured film obtained by thermosetting the photosensitive resin composition of the present invention includes various hard coat films such as a touch panel protective film, an insulating film for touch sensors, a planarizing film for TFTs of liquid crystals and organic EL displays, It is suitably used for metal wiring protective films, insulating films, antireflection films, antireflection films, optical filters, overcoats for color filters, pillar materials, and the like.

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Abstract

La présente invention a pour objet une composition de résine photosensible développable en milieu alcalin qui présente une excellente stabilité au stockage à l'état liquide et à l'enduction, qui ne présente pas de réduction des propriétés adhésives pendant le stockage et avec laquelle un film durci présentant une dureté élevée et d'excellentes transparence, résistance à la chaleur humide, résistance à la sueur synthétique, propriétés adhésives, résistance aux produits chimiques et résistance au vide peut être produit. A cet effet, la présente invention porte sur une composition de résine photosensible qui comprend une résine acrylique (A), un composé polymérisable par voie radicalaire (B), un initiateur de photopolymérisation (C), un composé chélate métallique (D) et un solvant (E), ladite résine acrylique ayant une structure issue d'un maléimide ayant une structure particulière.
PCT/JP2014/051249 2013-02-12 2014-01-22 Composition de résine photosensible, film protecteur ou film isolant obtenu par thermodurcissement de ladite composition, écran tactile utilisant ledit film et procédé de production pour ledit écran tactile WO2014125884A1 (fr)

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CN201480008215.6A CN104981737A (zh) 2013-02-12 2014-01-22 感光性树脂组合物、使其热固化而成的保护膜或绝缘膜、使用其的触摸面板及其制造方法
JP2014503896A JP6319082B2 (ja) 2013-02-12 2014-01-22 感光性樹脂組成物、それを熱硬化させてなる保護膜又は絶縁膜、それを用いたタッチパネル及びその製造方法
KR1020157017378A KR20150118582A (ko) 2013-02-12 2014-01-22 감광성 수지 조성물, 그것을 열경화시켜서 이루어지는 보호막 또는 절연막, 그것을 사용한 터치 패널 및 그 제조 방법

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JP2014197171A (ja) * 2013-03-05 2014-10-16 東レ株式会社 感光性樹脂組成物、保護膜及び絶縁膜並びにタッチパネル及びその製造方法
EP3321326A4 (fr) * 2015-07-06 2019-02-27 Mitsubishi Gas Chemical Company, Inc. Composition de résine, pré-imprégné, feuille de résine, plaque stratifiée recouverte d'une feuille métallique, et carte de circuit imprimé
WO2019059169A1 (fr) * 2017-09-22 2019-03-28 東レ株式会社 Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille
WO2020040092A1 (fr) * 2018-08-20 2020-02-27 Jsr株式会社 Procédé pour former un motif, et composition sensible au rayonnement
WO2020202691A1 (fr) * 2019-03-29 2020-10-08 太陽インキ製造株式会社 Composition de résine photosensible, film sec, produit durci, et composant électronique
WO2021033441A1 (fr) * 2019-08-20 2021-02-25 東京応化工業株式会社 Composition durcissable, produit durci ainsi que procede de formation de film isolant
CN114236966A (zh) * 2021-12-21 2022-03-25 潍坊星泰克微电子材料有限公司 用于干法刻蚀的丙烯酸酯类负性光刻胶膜及其制备方法
US11390766B2 (en) 2017-06-08 2022-07-19 Microcraft Korea Co., Ltd. Resin composition for inkjet printing and printed wiring board prepared by using same
US11698586B2 (en) 2018-03-23 2023-07-11 Merck Patent Gmbh Negative-working ultra thick film photoresist
KR20230141587A (ko) 2022-03-31 2023-10-10 아사히 가세이 가부시키가이샤 감광성 수지 조성물 및 감광성 엘리먼트

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WO2015129443A1 (fr) * 2014-02-26 2015-09-03 株式会社日本触媒 Composition de résine durcissable et utilisation associée
TWI512058B (zh) * 2014-12-25 2015-12-11 Chi Mei Corp 光硬化性塗佈組成物、光硬化塗佈膜及觸控面板
JP6714493B2 (ja) * 2015-12-24 2020-06-24 信越化学工業株式会社 有機膜形成用化合物、有機膜形成用組成物、有機膜形成方法、及びパターン形成方法
CN107957655A (zh) * 2016-10-18 2018-04-24 广州亦盛环保科技有限公司 一种3d盖板玻璃用负型感光性白色油墨及其制备方法、使用方法
KR102622684B1 (ko) * 2016-12-20 2024-01-10 솔브레인 주식회사 오버코팅 조성물 및 이를 이용하여 제조된 도전막
CN110419003B (zh) * 2017-03-17 2023-04-18 大阪有机化学工业株式会社 感光性树脂组合物
KR102254366B1 (ko) * 2017-03-28 2021-05-24 도레이 카부시키가이샤 감광성 수지 조성물, 경화막, 경화막을 구비하는 소자, 경화막을 구비하는 유기 el 표시 장치, 경화막의 제조 방법, 및 유기 el 표시 장치의 제조 방법
CN111133344A (zh) * 2017-09-26 2020-05-08 大阪有机化学工业株式会社 光间隔体形成用感光性树脂组合物、光间隔体的形成方法、带光间隔体的基板、及滤色器
CN112533707B (zh) * 2018-05-14 2023-09-05 Nbd纳米技术公司 有机硅烷涂布组合物
KR20210122066A (ko) * 2020-03-30 2021-10-08 동우 화인켐 주식회사 절연막 형성용 수지 조성물, 이를 이용하여 제조된 절연막, 화상표시장치 및 절연막 제조 방법

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005189399A (ja) * 2003-12-25 2005-07-14 Jsr Corp 感放射線性組成物、マイクロレンズとその形成方法および液晶表示素子
JP2008056867A (ja) * 2006-09-04 2008-03-13 The Inctec Inc 顔料分散液および着色感光性組成物
JP2009075591A (ja) * 2007-09-21 2009-04-09 Dongwoo Fine-Chem Co Ltd 着色感光性樹脂組成物、カラーフィルタ及びこれを備える液晶表示装置
JP2009163226A (ja) * 2007-12-14 2009-07-23 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2010027033A (ja) * 2008-06-19 2010-02-04 Jsr Corp タッチパネルの保護膜形成用感放射線性樹脂組成物とその形成方法
JP2010128275A (ja) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性フィルム及び永久レジスト
JP2010160419A (ja) * 2009-01-09 2010-07-22 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及びそれを用いた永久レジスト。
JP2010530441A (ja) * 2007-05-15 2010-09-09 エルジー・ケム・リミテッド 電磁波遮蔽層の製造時に無電解メッキに対する触媒前駆体樹脂組成物、これを用いた金属パターンの形成方法及びこれにより製造された金属パターン
JP2011039165A (ja) * 2009-08-07 2011-02-24 Hitachi Chem Co Ltd アルカリ可溶性光硬化型組成物、該組成物を使用した硬化塗膜及び透明部材
WO2011129210A1 (fr) * 2010-04-14 2011-10-20 東レ株式会社 Composition de résine photosensible négative, et film de protection et élément d'écran tactile utilisant une telle composition
JP2013205654A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp 着色感光性組成物、カラーフィルタ、カラーフィルタの製造方法、及び表示装置

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11106647A (ja) * 1997-10-08 1999-04-20 Toray Ind Inc ポリアミド樹脂組成物
JP2004177498A (ja) * 2002-11-25 2004-06-24 Nippon Shokubai Co Ltd 光硬化性樹脂組成物およびその用途
JP2006342278A (ja) * 2005-06-10 2006-12-21 Mitsubishi Engineering Plastics Corp ポリアミド樹脂組成物及び成形品
JP2010084007A (ja) * 2008-09-30 2010-04-15 Mitsubishi Engineering Plastics Corp 携帯電子機器用ポリアミド樹脂組成物及び携帯電子機器部品
JP5526868B2 (ja) * 2010-03-03 2014-06-18 Ｊｓｒ株式会社 感放射線性樹脂組成物、表示素子のスペーサーおよび保護膜ならびにそれらの形成方法
KR101761181B1 (ko) * 2010-06-09 2017-07-25 도레이 카부시키가이샤 감광성 실록산 조성물, 그것으로부터 형성된 경화막 및 경화막을 갖는 소자
JP5765235B2 (ja) * 2010-09-02 2015-08-19 東レ株式会社 感光性組成物、それから形成された硬化膜および硬化膜を有する素子

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005189399A (ja) * 2003-12-25 2005-07-14 Jsr Corp 感放射線性組成物、マイクロレンズとその形成方法および液晶表示素子
JP2008056867A (ja) * 2006-09-04 2008-03-13 The Inctec Inc 顔料分散液および着色感光性組成物
JP2010530441A (ja) * 2007-05-15 2010-09-09 エルジー・ケム・リミテッド 電磁波遮蔽層の製造時に無電解メッキに対する触媒前駆体樹脂組成物、これを用いた金属パターンの形成方法及びこれにより製造された金属パターン
JP2009075591A (ja) * 2007-09-21 2009-04-09 Dongwoo Fine-Chem Co Ltd 着色感光性樹脂組成物、カラーフィルタ及びこれを備える液晶表示装置
JP2009163226A (ja) * 2007-12-14 2009-07-23 Sumitomo Chemical Co Ltd 着色感光性樹脂組成物
JP2010027033A (ja) * 2008-06-19 2010-02-04 Jsr Corp タッチパネルの保護膜形成用感放射線性樹脂組成物とその形成方法
JP2010128275A (ja) * 2008-11-28 2010-06-10 Hitachi Chem Co Ltd 感光性樹脂組成物、これを用いた感光性フィルム及び永久レジスト
JP2010160419A (ja) * 2009-01-09 2010-07-22 Hitachi Chem Co Ltd 感光性樹脂組成物、感光性フィルム、レジストパターンの形成方法及びそれを用いた永久レジスト。
JP2011039165A (ja) * 2009-08-07 2011-02-24 Hitachi Chem Co Ltd アルカリ可溶性光硬化型組成物、該組成物を使用した硬化塗膜及び透明部材
WO2011129210A1 (fr) * 2010-04-14 2011-10-20 東レ株式会社 Composition de résine photosensible négative, et film de protection et élément d'écran tactile utilisant une telle composition
JP2013205654A (ja) * 2012-03-28 2013-10-07 Fujifilm Corp 着色感光性組成物、カラーフィルタ、カラーフィルタの製造方法、及び表示装置

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014197171A (ja) * 2013-03-05 2014-10-16 東レ株式会社 感光性樹脂組成物、保護膜及び絶縁膜並びにタッチパネル及びその製造方法
US11195638B2 (en) 2015-07-06 2021-12-07 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, resin sheet, metal foil-clad laminate, and printed circuit board
EP3321326A4 (fr) * 2015-07-06 2019-02-27 Mitsubishi Gas Chemical Company, Inc. Composition de résine, pré-imprégné, feuille de résine, plaque stratifiée recouverte d'une feuille métallique, et carte de circuit imprimé
US11769607B2 (en) 2015-07-06 2023-09-26 Mitsubishi Gas Chemical Company, Inc. Resin composition, prepreg, resin sheet, metal foil-clad laminate, and printed circuit board
US11390766B2 (en) 2017-06-08 2022-07-19 Microcraft Korea Co., Ltd. Resin composition for inkjet printing and printed wiring board prepared by using same
WO2019059169A1 (fr) * 2017-09-22 2019-03-28 東レ株式会社 Composition de résine photosensible transparente, photo-espaceur, dispositif d'affichage à cristaux liquides, procédé de production de photo-espaceur, procédé de production de dispositif d'affichage à cristaux liquides, et utilisation d'une composition de résine photosensible transparente pour exposition par balayage de lentille
CN111149058B (zh) * 2017-09-22 2024-03-08 东丽株式会社 透明感光性树脂组合物及其应用、光刻间隔物和液晶显示装置及其制造方法
CN111149058A (zh) * 2017-09-22 2020-05-12 东丽株式会社 透明感光性树脂组合物、光刻间隔物、液晶显示装置、光刻间隔物的制造方法、液晶显示装置的制造方法及透明感光性树脂组合物在透镜扫描曝光中的应用
JPWO2019059169A1 (ja) * 2017-09-22 2020-09-03 東レ株式会社 透明感光性樹脂組成物、フォトスペーサー、液晶表示装置、フォトスペーサーの製造方法、液晶表示装置の製造方法および透明感光性樹脂組成物のレンズスキャン露光への使用
US11698586B2 (en) 2018-03-23 2023-07-11 Merck Patent Gmbh Negative-working ultra thick film photoresist
WO2020040092A1 (fr) * 2018-08-20 2020-02-27 Jsr株式会社 Procédé pour former un motif, et composition sensible au rayonnement
WO2020202691A1 (fr) * 2019-03-29 2020-10-08 太陽インキ製造株式会社 Composition de résine photosensible, film sec, produit durci, et composant électronique
JP2021031541A (ja) * 2019-08-20 2021-03-01 東京応化工業株式会社 硬化性組成物、硬化物、及び絶縁膜の形成方法
WO2021033441A1 (fr) * 2019-08-20 2021-02-25 東京応化工業株式会社 Composition durcissable, produit durci ainsi que procede de formation de film isolant
JP7428491B2 (ja) 2019-08-20 2024-02-06 東京応化工業株式会社 硬化性組成物、硬化物、及び絶縁膜の形成方法
CN114236966A (zh) * 2021-12-21 2022-03-25 潍坊星泰克微电子材料有限公司 用于干法刻蚀的丙烯酸酯类负性光刻胶膜及其制备方法
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