WO2013146130A1 - Agent de couplage au silane, composition de résine photosensible, film durci et élément d'écran tactile - Google Patents

Agent de couplage au silane, composition de résine photosensible, film durci et élément d'écran tactile Download PDF

Info

Publication number
WO2013146130A1
WO2013146130A1 PCT/JP2013/056073 JP2013056073W WO2013146130A1 WO 2013146130 A1 WO2013146130 A1 WO 2013146130A1 JP 2013056073 W JP2013056073 W JP 2013056073W WO 2013146130 A1 WO2013146130 A1 WO 2013146130A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
resin composition
silane coupling
acid
photosensitive resin
Prior art date
Application number
PCT/JP2013/056073
Other languages
English (en)
Japanese (ja)
Inventor
荒木斉
諏訪充史
日比野利保
Original Assignee
東レ株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Publication of WO2013146130A1 publication Critical patent/WO2013146130A1/fr

Links

Images

Classifications

    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
    • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/20—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/16—Radicals substituted by singly bound hetero atoms other than halogen by oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • 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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
    • 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

Definitions

  • the present invention relates to a silane coupling agent, a photosensitive resin composition, a cured film, and a touch panel member.
  • a color filter for a liquid crystal display requires an overcoat for suppressing disorder in the alignment of the liquid crystal
  • a TFT substrate requires an organic passivation film called a planarization film to achieve a high aperture ratio.
  • a photosensitive transparent material is used.
  • Capacitive touch panels which are attracting attention with the spread of smartphones and tablet terminals, are placed at the intersections of ITO (Indium Tin Oxide) and metal (silver, molybdenum, aluminum, etc.) wiring formed on the sensor glass. Insulating films to be used and protective films for protecting them are required, and photosensitive transparent materials are often used for these films.
  • the characteristics required for these photosensitive transparent materials vary depending on the process, but include pattern processability, transparency, adhesion to the base substrate, chemical resistance, heat resistance, and high temperature and high humidity resistance. Among them, pattern processability and chemical resistance are important characteristics in production yield, and adhesiveness of the cured film is an important characteristic in product quality.
  • pattern processing When processing to metal base substrates used for TFT substrates and touch panels, pattern processing The problems of peeling off of the pattern, floating, and the problem of adhesion to the base substrate after the thermosetting treatment and chemical treatment have always been problems of the photosensitive transparent material.
  • the most studied method for improving the adhesion between the resin and the substrate is the addition of a silane coupling agent.
  • a diurea-type silane coupling agent has been proposed in order to suppress development peeling when a negative photosensitive polybenzoxazole precursor composition is processed into a silicon wafer (Patent Document 1).
  • the silane coupling agent which has an imide group (patent document 2)
  • the silane coupling agent which has a carboxyl group and an ester group or an amide group (patent document 3)
  • a polymeric group and a urethane group Containing silane coupling agents
  • JP 2002-179688 A International Publication No. 2009/096050 JP 2006-316032 A JP 2004-205615 A JP-A-62-249992 Japanese Patent Laid-Open No. 5-287215
  • Patent Document 1 Since Patent Document 1 has basicity and Patent Document 3 has an acidic group, the storage stability of the composition remains as a problem.
  • Patent Document 2 since it has an imide group, a reduction in transmittance has been a problem.
  • the urethane group-containing silane coupling agents as in Patent Documents 4 to 6 have a problem in heat resistance.
  • compounds such as tin that are likely to be toxic at the time of synthesis are often required as catalysts, and so much research has not been conducted.
  • any silane coupling agent improves adhesion on plastic substrates, silicon substrates, glass substrates, etc., and is not effective in improving pattern peeling on metal substrates such as ITO and adhesion of cured films. It was enough.
  • the present invention is excellent in pattern peeling and floating during development, not only for plastic substrates, silicon substrates, and glass substrates, but also for metal substrates.
  • Silane coupling agent that exhibits an improvement effect exhibits an improvement effect excellent in adhesion to the base substrate after heat curing treatment or chemical treatment, has heat resistance, and does not require a compound that is toxic during synthesis It is a problem to provide.
  • the inventors have found that the specific silane coupling agent does not cause pattern peeling or floating during development, and has good adhesion to the base substrate after thermosetting or chemical treatment. It has been found that a negative photosensitive resin composition and a positive photosensitive resin composition can be obtained.
  • the object of the present invention is achieved by (A) a silane coupling agent characterized by being represented by the general formula (1).
  • the object of the present invention includes (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D) a photoradical polymerization initiator. (I) It is achieved by a negative photosensitive resin composition.
  • the object of the present invention is achieved by (II) a positive photosensitive resin composition containing (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, and (E) a quinonediazide compound. It is what is done.
  • the object of the present invention is achieved by a touch panel member having a cured film obtained by curing the above-mentioned (I) negative photosensitive resin composition or (II) positive photosensitive resin composition.
  • the object of the present invention is achieved by a TFT substrate having a cured film obtained by curing the above-mentioned (I) negative photosensitive resin composition or (II) positive photosensitive resin composition.
  • silane coupling agent of the present invention By adding the silane coupling agent of the present invention to the resin composition, there is no occurrence of pattern peeling or floating during development, and a cured film with good adhesion to the base substrate after thermal curing or chemical treatment is obtained. Obtainable.
  • silane coupling agent of the present invention is represented by the general formula (1).
  • R 1 independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group, or a substituent thereof.
  • R 2 each independently represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or a substituent thereof.
  • R 3 represents a divalent organic group having 1 to 30 carbon atoms,
  • R 4 represents a monovalent organic group having 1 to 30 carbon atoms having a heterocyclic structure, and
  • m represents 0 to 2 Represents an integer.
  • the silane coupling agent represented by the general formula (1) has heat resistance higher than that of a normal urethane compound, and brings about an effect of improving adhesiveness between various resins and metals.
  • the silane coupling agent represents a compound containing hydrolyzable silicon, and is a compound that generates a silanol group by reaction with water.
  • the hydrolyzable group include an alkoxy group, an acetoxy group, a phenoxy group, and a chloro group.
  • R 1 is preferably a methyl group, an ethyl group, a butyl group, a methoxyethyl group or a phenyl group, and particularly preferably a methyl group or an ethyl group from the viewpoint of obtaining raw materials.
  • R 2 is preferably a methyl group, an ethyl group, a butyl group or a phenyl group, and particularly preferably a methyl group or a phenyl group from the viewpoint of obtaining raw materials.
  • R 3 is preferably an organic group represented by the following general formula (2) or the following general formula (3) having a methylene moiety, represented by a propylene group, a butylene group, a pentylene group, a hexylene group or the general formula (3).
  • the organic group to be used is more preferable because it has a large effect of improving adhesiveness.
  • R 4 an organic group represented by the following general formula (4), furanyl group, pyranyl group, dihydropyranyl group, thienyl group, tetrahydrothiofuranyl group, benzofuranyl group, isobenzofuranyl group, imidazolyl group, A pyrrolyl group, a pyridyl group, a pyrrolidyl group, a piperidyl group, a thiazolyl group, an oxazolyl group, a 2,3-epoxycyclohexyl group, or a substituted product thereof is preferable.
  • the general formula (4) Is more preferably an organic group represented by the formula: furanyl group, pyranyl group, dihydropyranyl group, thienyl group, tetrahydrothiofuranyl group or 2,3-epoxycyclohexyl group, and the organic group represented by the general formula (4) is Further preferred.
  • R 5 represents hydrogen or an alkyl group having 1 to 10 carbon atoms.
  • R 5 include hydrogen, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, pentyl group, and hexyl group.
  • Examples of the organic group represented by the general formula (4) include an epoxy group, 2-methylepoxy group, oxetanyl group, 3-methyloxetanyl group, 3-ethyloxetanyl group, tetrahydrofuranyl group, 2-methyltetrahydrofuranyl group, and tetrahydro group.
  • a pyranyl group is preferable, and an epoxy group, a 3-methyloxetanyl group, a 3-ethyloxetanyl group, or a tetrahydrofuranyl group is more preferable from the viewpoint of obtaining raw materials.
  • Examples of the (A) silane coupling agent represented by the general formula (1) include glycidyl (3- (trimethoxysilyl) propyl) carbamate, glycidyl (3- (triethoxysilyl) propyl) carbamate, glycidyl (3 -(Methyldimethoxysilyl) propyl) carbamate, glycidyl (3- (trimethoxysilyl) butyl) carbamate, glycidyl (2-((3-trimethoxysilylpropyl) amino) ethyl) carbamate, oxetanyl (3- (trimethoxysilyl) ) Propyl) carbamate, oxetanyl (3- (triethoxysilyl) propyl) carbamate, oxetanyl (3- (triethoxysilyl) propyl) carbamate, oxetanyl (3- (methyldimethoxys
  • the method for synthesizing the silane coupling agent represented by the general formula (1) is not particularly limited, and examples thereof include a method of synthesizing by a reaction between a hydrolyzable silane-containing isocyanate compound and an alcohol compound.
  • the isocyanate compound include trimethoxysilylpropyl isocyanate, triethoxysilylpropyl isocyanate, trimethoxysilylbutyl isocyanate, triethoxysilylbutyl isocyanate, trimethoxysilylpentyl isocyanate, triethoxysilylpentyl isocyanate, trimethoxysilylpentyl isocyanate, trimethoxysilylpentyl isocyanate, trimethoxysilylpentyl isocyanate, trimethoxysilylpentyl isocyanate, Ethoxysilylpentyl isocyanate, 4-trimethoxysilylphenyl iso
  • Examples of the alcohol compound include glycidol, 2-methylglycidol, oxetanylmethanol, 2-methyloxetanylmethanol, 2-ethyloxetanylmethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, tetrahydropyranyl alcohol, pyrrolidinemethanol, N-methyl- Examples include pyrrole methanol, 1-methyl-2-pyrrolidinemethanol pyridinemethanol, 6-methylpyridinemethanol or thienylmethanol, but 2-methyloxetanylmethanol, 2-ethyloxetanylmethanol or tetrahydrofurfurylalcohol are available and stored. It is preferable in terms of stability.
  • the reaction between the isocyanate compound and the alcohol compound may be carried out without a catalyst or a catalyst, but a non-catalytic reaction that does not include a catalyst removal step is preferred.
  • the catalyst used include dibutyltin laurate, tetrabutoxytitanium, tetraisopropoxytitanium, tetrakisacetylacetonatotitanium, and tetrakisacetylacetonatozirconium.
  • the negative photosensitive resin composition (I) of the present invention comprises (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, and (D). Contains a radical photopolymerization initiator.
  • the (II) positive photosensitive resin composition of the present invention contains (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, and (E) a quinonediazide compound.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention contain (A) a silane coupling agent represented by the general formula (1).
  • a silane coupling agent represented by the general formula (1).
  • peeling and penetration can be suppressed when alkali development is performed on a metal substrate.
  • membrane after thermosetting will have favorable adhesiveness to a metal substrate.
  • the preferred range and specific examples of the (A) silane coupling agent are as described above.
  • the amount of (A) silane coupling agent added is preferably 0.1 to 20 parts by weight when the sum of (B) alkali-soluble resin and (C) polyfunctional acrylic monomer is 100 parts by weight. If the amount is less than 0.1 parts by weight, the adhesion improving effect may not be sufficiently exhibited. If the amount exceeds 20 parts by weight, the developability may be deteriorated.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention contain (B) an alkali-soluble resin.
  • alkali-soluble resin Polysiloxane, an acrylic resin, or a polyester resin is preferable from a transparency and versatility viewpoint.
  • the carboxylic acid equivalent of the polysiloxane is not particularly limited, but is preferably 200 to 1,400 g / mol because a good balance between film reduction and development peeling can be obtained. Moreover, it is preferable that it has an ethylenically unsaturated bond from the point of the improvement of the exposure sensitivity at the time of using as a base polymer of (I) negative photosensitive resin composition, and the hardness improvement of the cured film obtained.
  • the double bond equivalent of the polysiloxane is not particularly limited, but it is preferably 150 to 10,000 g / mol because a good balance of hardness and resolution can be obtained. Moreover, it is preferable from a viewpoint of storage stability to have an aryl group.
  • the carboxylic acid equivalent represents the weight of the resin necessary to obtain 1 mol amount of carboxyl groups, and the unit is g / mol.
  • the double bond equivalent represents the weight of the resin necessary to obtain 1 mol amount of the double bond group, and the unit is g / mol.
  • the method for synthesizing the polysiloxane is not particularly limited, but a general method is that the organosilane compound is hydrolyzed and the hydrolyzate is condensed.
  • the conditions for the hydrolysis reaction can be set as appropriate. For example, after adding an acid catalyst and water to the organosilane compound in a solvent over 1 to 180 minutes, the reaction is performed at room temperature to 110 ° C. for 1 to 180 minutes. It is preferable. By performing the hydrolysis reaction under such conditions, a rapid reaction can be suppressed.
  • the reaction temperature is preferably 30 to 105 ° C.
  • the hydrolysis reaction is preferably performed in the presence of an acid catalyst.
  • an acidic aqueous solution containing formic acid, acetic acid or phosphoric acid is preferable.
  • the content of these acid catalysts is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the total organosilane compound used in the hydrolysis reaction.
  • the conditions for the condensation reaction are, for example, that the silanol compound is obtained by the hydrolysis reaction of the organosilane compound as described above, and then the reaction solution is heated as it is at 50 ° C. or higher and below the boiling point of the solvent for 1 to 100 hours to be reacted. It is preferable.
  • reheating or a base catalyst may be added. Further, after hydrolysis according to the purpose, a suitable amount of the produced alcohol may be distilled and removed under heating and / or reduced pressure, and then a suitable solvent may be added.
  • organosilane compound used for the synthesis of polysiloxane there is no particular limitation on the organosilane compound used for the synthesis of polysiloxane, but for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyl Triethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1-naphthyltrimethoxysilane, 2-naphthyltrimethoxysilane, 1-naphthyltriethoxysilane, 2-naphthyltriethoxysilane 3-amin
  • the carboxylic acid equivalent of polysiloxane can be calculated by measuring the acid value after calculating the silanol group / carboxyl group ratio in polysiloxane by 1 H-NMR and IR.
  • the double bond equivalent can be calculated by measuring the iodine value.
  • the weight average molecular weight (Mw) of the polysiloxane is not particularly limited, but is preferably 1,000 to 100,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.
  • the acrylic resin is not particularly limited, but a carboxyl group-containing acrylic resin is preferable from the viewpoint of alkali developability.
  • the carboxylic acid equivalent of the acrylic resin is not particularly limited, but is preferably 200 to 1400 g / mol, more preferably 300 g to 1200 g / mol, and further preferably 400 to 800 g / mol.
  • a negative photosensitive resin composition after development with an alkaline aqueous solution can be suppressed and film loss in the exposed area can be suppressed, and a good pattern can be formed. it can.
  • An ethylenically unsaturated double bond group is introduced into at least a part of the acrylic resin.
  • (I) Improvement of sensitivity and hardness of cured film when used as a base polymer of a negative photosensitive resin composition Is preferable.
  • the double bond equivalent of the acrylic resin is not particularly limited, but is preferably 150 to 10,000 g / mol. By being in the above range, both hardness and crack resistance can be achieved at a high level.
  • the double bond equivalent can be calculated by measuring the iodine value.
  • the acrylic resin may form a branched structure. By forming the branched structure, the hardness and chemical resistance of the cured film can be improved.
  • radical polymerization of the (meth) acrylic compound is preferable.
  • the (meth) acrylic compound include a carboxyl group and / or an acid anhydride group-containing (meth) acrylic compound or other (meth) acrylic acid ester.
  • the catalyst for radical polymerization is not particularly limited, and azo compounds such as azobisisobutyronitrile and organic peroxides such as benzoyl peroxide are generally used. The conditions for radical polymerization can be appropriately set.
  • a carboxyl group and / or an acid anhydride group-containing (meth) acrylic compound, other (meth) acrylic acid ester and a radical polymerization catalyst are added in a solvent. It is preferable that the reaction vessel is sufficiently purged with nitrogen by bubbling or vacuum degassing, and then reacted at 60 to 110 ° C. for 30 to 300 minutes.
  • an acid anhydride group-containing (meth) acrylic compound it is preferable to add a theoretical amount of water and react at 30 to 60 ° C. for 30 to 60 minutes.
  • chain transfer agents such as a thiol compound, as needed.
  • Examples of the (meth) acrylic compound used for the synthesis of the acrylic resin include (meth) acrylic acid, (meth) acrylic anhydride, itaconic acid, itaconic anhydride, succinic acid mono (2-acryloyloxyethyl), Mono (2-acryloyloxyethyl) phthalate, mono (2-acryloyloxyethyl) tetrahydrophthalate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclo (meth) acrylate Propyl, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, (meth) 2-cyclopentyloxyca acrylate Bony
  • the acrylic resin may use other unsaturated double bond-containing monomer as a copolymerization monomer.
  • Other unsaturated double bond-containing monomers include, for example, styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ⁇ -methylstyrene, maleic anhydride, norbornene, norbornene dicarboxylic acid, norbornene dicarboxylic acid anhydride
  • Product cyclohexene, butyl vinyl ether, butyl allyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxyethyl allyl ether, cyclohexane vinyl ether, cyclohexane allyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxybutyl allyl ether, allyl glycidyl ether, vinyl glycidyl Ether, o-vinylbenzyl glycidy
  • examples of the acrylic resin include the above-mentioned carboxyl group or acid anhydride group-containing (meth) acrylic compound and (meth) acrylic acid ester and / or other unsaturated double bonds.
  • Those obtained by radical polymerization of a bond-containing monomer and then addition reaction of an epoxy compound having an ethylenically unsaturated double bond group are preferred.
  • the catalyst used for the addition reaction of the epoxy compound having an ethylenically unsaturated double bond group is not particularly limited, and a known catalyst can be used.
  • Amino-based catalysts such as phenol and dimethylbenzylamine
  • tin-based catalysts such as tin 2-ethylhexanoate (II) and dibutyltin laurate
  • titanium-based catalysts such as titanium 2-ethylhexanoate (IV)
  • phosphorus-based catalysts such as acetylacetonate chromium or chromium chloride.
  • Examples of the epoxy compound having an ethylenically unsaturated double bond group include glycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, ⁇ -n-propylglycidyl (meth) acrylate, and (meth) acrylic.
  • the branched acrylic resin can be obtained by using a compound having a plurality of ethylenically unsaturated double bond groups and / or thiol groups during polymerization.
  • the compound having a plurality of ethylenically unsaturated double bond groups include glycerol diacrylate, glycerol dimethacrylate, glycerol acrylate methacrylate, glycerol triacrylate, glycerol trimethacrylate, glycerol diacrylate methacrylate, glycerol acrylate dimethacrylate, divinylbenzene , Trivinylbenzene, diethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane diacrylate or trimethylolpropane triacrylate.
  • Examples of the compound having a plurality of thiol groups include pentaerythritol, tetrakis (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, or 1 , 3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione.
  • the weight average molecular weight (Mw) of the acrylic resin is not particularly limited, but is preferably 2,000 to 200,000 in terms of polystyrene measured by gel permeation chromatography (GPC). By setting Mw within the above range, good coating characteristics can be obtained, and the solubility in a developer during pattern formation is also good.
  • the polyester is not particularly limited, but it is easy to synthesize what is obtained through a polyaddition reaction between a polyfunctional epoxy compound and a polycarboxylic acid compound or a polyaddition reaction between a polyol compound and a dianhydride. , Because there are few side reactions.
  • a polyol compound since it is easy to introduce a radical polymerizable group and an aromatic ring, those obtained by a reaction between a polyfunctional epoxy compound and a radical polymerizable group-containing monobasic acid compound are preferable.
  • a polyfunctional epoxy compound is added in an amount of 1.01 to 2 equivalents relative to the polyvalent carboxylic acid compound for polymerization, and then a radical polymerizable group-containing monobasic acid compound is added to the terminal epoxy site, Examples include a method of adding an acid anhydride to the hydroxyl group to be generated.
  • a polyol compound As a method of undergoing a polyaddition reaction between a polyol compound and a dianhydride, for example, in the presence of a catalyst, a polyol compound) a dianhydride is polymerized at an arbitrary ratio, and then a part of the generated carboxyl group
  • the method of adding a radically polymerizable group containing epoxy compound is mentioned.
  • a polyol compound has a radically polymerizable group, it does not need to add a radically polymerizable group containing epoxy compound.
  • Examples of the catalyst used for the polyaddition reaction and the addition reaction include ammonium-based catalysts such as tetrabutylammonium acetate, amino-based catalysts such as 2,4,6-tris (dimethylaminomethyl) phenol or dimethylbenzylamine, and triphenylphosphine. Or a phosphorus catalyst such as acetylacetonate chromium or chromium chloride.
  • the polyfunctional epoxy compound is preferably a compound represented by the following general formula (5) in order to adjust the refractive index of a cured film and improve chemical resistance.
  • R 6 and R 7 each independently represent hydrogen, an alkyl or cycloalkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a group in which they are substituted, or R 6 And R 7 together represent a cycloalkyl group having 2 to 12 carbon atoms, an aromatic ring having 5 to 12 carbon atoms or a group in which they are substituted, and R 8 and R 9 are each independently hydrogen, A C 2-12 alkyl group, a C 6-20 aryl group, or a group in which they are substituted, p and q each independently represent an integer of 0-10.
  • R 6 , R 7 , R 8 and R 9 include, for example, a methyl group, an ethyl group, a propyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group, a naphthyl group, an o-tolyl group, a biphenyl
  • R 6 and R 7 may form a cyclic structure.
  • the cyclic structure is preferably a 5- to 7-membered ring. Examples of the cyclic structure formed by R 6 and R 7 include the substituents shown below.
  • Examples of the polyfunctional epoxy compound include the following compounds.
  • polyvalent carboxylic acid compound examples include succinic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2,2′-biphenyldicarboxylic acid or 4, 4'-biphenyldicarboxylic acid is exemplified, but phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, 2,2'-biphenyldicarboxylic acid are used to improve chemical resistance and insulation properties of cured films and the like. Acid or 4,4′-biphenyldicarboxylic acid is preferred.
  • polyol compound examples include aliphatic alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, glycerin, trimethylolpropane, and pentaerythritol, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, Compounds obtained by reaction of a functional epoxy compound with a radical polymerizable group-containing monobasic acid compound or compounds obtained by reaction of a bisphenol compound represented by the following general formula (6) with a radical polymerizable group-containing epoxy compound, etc. Although an aromatic alcohol compound is mentioned, an aromatic alcohol compound is preferable.
  • R ⁇ 6 >, R ⁇ 7> , R ⁇ 8 > and R ⁇ 9 > in General formula (6) are the same as General formula (5).
  • dianhydride examples include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3 3'-benzophenonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) hexafluoro Propandioic anhydride, 1,1-bis (3,4-dicarboxyphenyl) ethanedioic anhydride, 1,1-bis (2,3-dicarboxyphenyl) e
  • Heptanetetracarboxylic dianhydride bicyclo [3.3.1. ] Tetracarboxylic dianhydride, bicyclo [3.1.1. ] Hept-2-enetetracarboxylic dianhydride, bicyclo [2.2.2. ]
  • Aliphatic tetracarboxylic dianhydrides such as octane tetracarboxylic dianhydride or adamantane tetracarboxylic dianhydride may be mentioned. In order to improve chemical resistance and insulation properties of cured films, etc.
  • Is pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 2 ′, 3,3′-biphenyltetracarboxylic dianhydride is preferable, and in order to improve the transparency of a cured film or the like, cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclo Pentanetetracarboxylic dianhydride or cyclohexanetetracarboxylic dianhydride is preferred.
  • Examples of the radically polymerizable group-containing monobasic acid compound include (meth) acrylic acid, succinic acid mono (2- (meth) acryloyloxyethyl), phthalic acid mono (2- (meth) acryloyloxyethyl), tetrahydrophthal Examples include acid mono (2- (meth) acryloyloxyethyl) or p-hydroxystyrene.
  • radical polymerizable group-containing epoxy compound examples include glycidyl (meth) acrylate, ⁇ -ethylglycidyl (meth) acrylate, ⁇ -n-propyl glycidyl (meth) acrylate, and ⁇ -n- (meth) acrylate.
  • acid anhydrides examples include succinic acid anhydride, maleic acid anhydride, itaconic acid anhydride, phthalic acid anhydride, trimellitic acid anhydride, pyromellitic acid monoanhydride, and 2,3-biphenyldicarboxylic acid anhydride. 3,4-biphenyldicarboxylic anhydride, hexahydrophthalic anhydride, glutaric anhydride, 3-methylphthalic anhydride, norbornene dicarboxylic anhydride, cyclohexene dicarboxylic anhydride or 3-trimethoxysilylpropyl succinic acid Anhydrides are mentioned.
  • the content of the (B) alkali-soluble resin in the (I) negative photosensitive resin composition of the present invention is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application.
  • the negative photosensitive resin composition of the present invention contains (C) a polyfunctional monomer.
  • the polymerization of (C) polyfunctional monomer proceeds with the following (D) photopolymerization initiator by light irradiation, and the exposed portion of the (I) negative photosensitive resin composition of the present invention is insolubilized in the alkaline aqueous solution, A pattern of the mold can be formed.
  • the polyfunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule, and is not particularly limited, but a polyfunctional monomer having a (meth) acryl group that is easily radically polymerized is used. preferable. Moreover, it is preferable from the point of a sensitivity and hardness that the double bond equivalent of (C) polyfunctional monomer is 80 g / mol or more and 400 g / mol or less.
  • the polyfunctional monomer for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylol Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,3-butanediol diacrylate, 1,3-butanediol dimethacrylate, neopentyl glycol diacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, dimethylol-tricyclo
  • pentaerythritol tetraacrylate dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate or tripentaerythritol octaacrylate is preferred
  • dimethylol-tricyclodecane diacrylate is preferred from the viewpoint of improving hydrophobicity.
  • the content of the (C) polyfunctional monomer is not particularly limited and can be arbitrarily selected depending on the desired film thickness and application.
  • the sum of the resin and the polyfunctional monomer (C) is 100 parts by weight, 10 to 60 parts by weight is common.
  • the (I) negative photosensitive resin composition of the present invention contains (D) a photopolymerization initiator.
  • the photopolymerization initiator is preferably one that decomposes and / or reacts with light (including ultraviolet rays and electron beams) to generate radicals.
  • photopolymerization initiator examples include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4 -Morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,4,6-trimethylbenzoylphenylphosphine Oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl) -phosphine oxide, 1-phenyl-1, 2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)
  • ⁇ -aminoalkylphenone compounds acylphosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group, or benzoic acid ester compounds having an amino group are preferable.
  • Examples of the ⁇ -aminoalkylphenone compound include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1.
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, or bis (2,6-dimethoxybenzoyl)-(2 , 4,4-trimethylpentyl) -phosphine oxide.
  • oxime ester compounds examples include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (O— Benzoyloxime)], 1-phenyl-1,2-butadion-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime or ethanone, 1- [9- And ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime).
  • 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 p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, and ethyl p-diethylaminobenzoate.
  • the content of the (D) photopolymerization initiator is not particularly limited, but the sum of (B) the alkali-soluble resin and (C) the polyfunctional monomer is 100. In the case of parts by weight, it is preferably 0.1 to 20 parts by weight. By setting it as the said range, hardening can fully be advanced and elution of the residual polymerization initiator etc. can be prevented and solvent resistance can be ensured.
  • the (II) positive photosensitive resin composition of the present invention contains (E) a quinonediazide compound.
  • E) The photosensitive composition containing a quinonediazide compound forms a positive type in which the exposed portion is removed with a developer.
  • the addition amount of the quinonediazide compound to be used is not particularly limited, but is preferably 3 to 30% by weight, more preferably 4 to 15% by weight with respect to (B) the alkali-soluble resin.
  • the addition amount of the quinonediazide compound is less than 3 wt%, the dissolution contrast between the exposed part and the unexposed part is too low, so that there is no realistic photosensitivity. In order to obtain a better dissolution contrast, 4 wt% or more is preferable.
  • the addition amount of the quinonediazide compound is more than 30 wt%, whitening of the coating film occurs due to poor compatibility between the alkali-soluble resin and the quinonediazide compound, or coloring due to decomposition of the quinonediazide compound that occurs during thermal curing is remarkable. Therefore, the colorless transparency of the cured film is lowered.
  • the quinonediazide compound to be used is not particularly limited, but a compound in which a naphthoquinonediazidesulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is preferable, and the ortho-position and para-position of the phenolic hydroxyl group of the compound are each independently hydrogen or a general formula ( The compound which is a substituent represented by 5) is more preferable.
  • R 10 to R 12 each independently represents an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group or a substituted phenyl group. Also, R 10 and R 11 , R 10 and R 12 or R 11 and (R 12 may form a cyclic structure.)
  • R 10 to R 12 are an alkyl group having 1 to 10 carbon atoms, the alkyl group may have a substituent or may be an unsubstituted product having no substituent. It can be selected according to the characteristics of the object.
  • alkyl group having 1 to 10 carbon atoms examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group, n- A heptyl group, an n-octyl group, a trifluoromethyl group or a 2-carboxyethyl group may be mentioned.
  • a substituent substituted by a phenyl group a hydroxyl group is mentioned, for example.
  • R 10 and R 11 , R 10 and R 12 or R 11 and R 12 may form a ring.
  • the cyclic structure formed examples include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and fluorene. A ring is mentioned.
  • quinonediazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinonediazidesulfonic acid chloride.
  • Examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).
  • 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used. Since 4-naphthoquinonediazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region, it is suitable for i-line exposure. Further, the 5-naphthoquinonediazide sulfonic acid ester compound has absorption in a wide wavelength range and is therefore suitable for exposure in a wide wavelength range.
  • a 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazide sulfonic acid ester compound may be mixed and used.
  • the molecular weight of the naphthoquinone diazide compound is preferably 300 to 1500, and more preferably 350 to 1200. If the molecular weight of the naphthoquinone diazide compound is greater than 1500, pattern formation may not be possible with an addition amount of 4 to 10 wt%. On the other hand, when the molecular weight of the naphthoquinone diazide compound is less than 300, the colorless transparency may be lowered.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention may contain (F) metal oxide particles.
  • F) metal oxide particles By containing metal oxide particles, the refractive index can be adjusted to a desired range. Further, the hardness, scratch resistance and crack resistance of the cured film can be further improved.
  • the number average particle diameter of the metal oxide particles is preferably 1 to 200 nm. In order to obtain a cured film having a high transmittance, the number average particle diameter is more preferably 1 to 70 nm.
  • the number average particle diameter of the metal oxide particles can be measured by a gas adsorption method, a dynamic light scattering method, an X-ray small angle scattering method, a transmission electron microscope, or a scanning electron microscope.
  • metal oxide particles (F) examples include silicon oxide particles, aluminum oxide particles, tin oxide particles, titanium oxide particles, zirconium oxide particles, or barium oxide particles. You can choose an appropriate one.
  • titanium oxide particles such as titanium oxide particles or barium titanate particles or zirconium oxide particles such as zirconium oxide particles are preferable for obtaining a cured film having a high refractive index.
  • silica particles examples include IPA-ST or MIBK-ST having a number average particle diameter of 12 nm, IPA-ST-L having a number average particle diameter of 45 nm, IPA-ST-ZL having a number average particle diameter of 100 nm, or number average particles.
  • PGM-ST having a diameter of 15 nm (all of which are manufactured by Nissan Chemical Industries, Ltd.), Oscar (registered trademark) 101 having a number average particle diameter of 12 nm, 105 having a number average particle diameter of 60 nm, and 106 having a number average particle diameter of 120 nm.
  • Cataloid (registered trademark) -S having a number average particle diameter of 5 to 80 nm (all of which are manufactured by Catalytic Chemical Industry Co., Ltd.), Quattron (registered trademark) PL-2L-PGME having a number average particle diameter of 16 nm, number average particle
  • the same PL-2L-BL, the same PL-2L-DAA with a diameter of 17 nm, or the same PL-2L or GP-2L with a number average particle diameter of 18-20 nm all Chemical Co., Ltd.
  • number average particle diameter 100nm of silica (SiO 2) SG-SO100 (KCM Co.) or the number average particle diameter of 5 ⁇ 50 nm Reolosil (R) (Co. Tokuyama).
  • the hollow silica particles include “Optlake” TR-113.
  • the content of the metal oxide particles is not particularly limited and may be an appropriate amount depending on the application, but is generally about 1 to 70 wt% in the solid content of the resin composition.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention may contain other silane coupling agents. By containing another silane coupling agent, the adhesion to the substrate is improved.
  • silane coupling agents examples include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, and n-propyl.
  • the addition amount of the silane coupling agent is not particularly limited, but is preferably in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin. When the addition amount is less than 0.1 parts by weight, the effect of improving the adhesiveness is not sufficient, and when it is more than 10 parts by weight, the silane coupling agents undergo a condensation reaction during storage, causing undissolved residue during development.
  • the (I) negative photosensitive resin composition and the (II) positive photosensitive resin composition of the present invention may contain various curing agents that accelerate the curing of the resin composition or facilitate the curing.
  • the curing agent is not particularly limited and known ones can be used. For example, nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds or polymers thereof, methylolated melamine derivatives, or methylol. And urea derivatives. Two or more of these may be contained. Of these, a metal chelate compound, a methylolated melamine derivative or a tyrolated urea derivative is preferred from the viewpoint of stability of the curing agent, processability of the obtained coating film, and the like.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber By containing an ultraviolet absorber, the light resistance of the resulting cured film is improved, and the resolution after development is improved in applications that require pattern processing.
  • the ultraviolet absorber is not particularly limited and known ones can be used, but benzotriazole compounds, benzophenone compounds or triazine compounds are preferred from the viewpoint of transparency and non-coloring properties.
  • UV absorbers for benzotriazole compounds include 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol or 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole.
  • Examples of the ultraviolet absorber of the benzophenone compound include 2-hydroxy-4-methoxybenzophenone.
  • Examples of the ultraviolet absorber of the triazine compound include 2- (4,6-diphenyl-1,3,5 triazin-2-yl) -5-[(hexyl) oxy] -phenol.
  • the (I) negative photosensitive resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a suitable amount of a polymerization inhibitor, the resolution after development is improved.
  • the polymerization inhibitor is not particularly limited, and known ones can be used, and examples thereof include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, hydroquinone methyl ether, 1,4-benzoquinone, and t-butylcatechol.
  • Examples of commercially available polymerization inhibitors include IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, and 565. Or the same 295 (all are BASF product). *
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention may contain a solvent.
  • a compound having an alcoholic hydroxyl group or a cyclic compound having a carbonyl group is preferred in that each component can be dissolved uniformly and the transparency of the resulting coating film can be improved. Two or more of these may be used.
  • a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable. By setting the boiling point to 110 ° C. or higher, drying proceeds moderately at the time of coating, and a good coating without uneven coating can be obtained. On the other hand, when the boiling point is 250 ° C. or lower, the amount of residual solvent in the film can be reduced, and film shrinkage during thermosetting can be further reduced, so that better flatness can be obtained.
  • Examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include, for example, acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone , 5-hydroxy-2-pentanone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether , Propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol or 3-methyl-3-methoxy-1-butanol.
  • diacetone alcohol may be used.
  • Propylene glycol monobutyl t- butyl ether is preferred from the viewpoint of the difference coverage.
  • Examples of the cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include, for example, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cyclohexane Although heptanone is mentioned, ⁇ -butyrolactone is preferred.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention may contain a solvent other than the above.
  • the solvent other than the above include ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether or diethyl ether, methyl ethyl ketone, acetyl acetone, methyl propyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexane Ketones such as pentanone or 2-heptanone, amides such as dimethylformamide or dimethylacetamide, or ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl Acetate or
  • the content of the solvent is not particularly limited, and any amount can be used depending on the coating method.
  • it is generally 50 to 95 wt% of the entire (I) negative photosensitive resin composition.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention are various types such as a fluorine-based surfactant or a silicone-based surfactant in order to improve the flow property during coating.
  • a surfactant may be contained.
  • surfactant for example, MegaFace (registered trademark) F142D, F172, F173, F183, F445, F470, F475 or F477 (all of which are Dainippon Ink Chemical, Inc.) INDUSTRIAL CO., LTD.) Or fluorine-based surfactants such as NBX-15 or FTX-218 (all of which are manufactured by Neos), BYK-333, BYK-301, BYK-331, BYK-345 or BYK -307 (all of which are manufactured by Big Chemie Japan Co., Ltd.), silicone surfactants, polyalkylene oxide surfactants or poly (meth) acrylate surfactants. Two or more of these may be used.
  • the (I) negative photosensitive resin composition and the (II) positive photosensitive resin composition of the present invention contain additives such as a dissolution inhibitor, a stabilizer, or an antifoaming agent as necessary. You can also.
  • the solid content concentration of the (I) negative photosensitive resin composition of the present invention is not particularly limited, and any amount of solvent or solute can be used depending on the coating method and the like.
  • the solid content concentration is generally 5 to 50 wt%.
  • (II) positive type photosensitive resin composition of this invention for example, after adding (E) quinonediazide compound and other additives to arbitrary solvents, and making it stir and dissolve, (A) Silane coupling agent represented by formula (1) and (B) alkali-soluble resin are added and further stirred for 20 minutes to 3 hours. The obtained solution is filtered to obtain (II) a positive photosensitive resin composition.
  • the (I) negative photosensitive resin composition or (II) positive photosensitive resin composition of the present invention is applied to microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, etc. It apply
  • a stepper mirror projection mask aligner (MPA) or parallel light mask aligner (hereinafter referred to as “PLA”)
  • light of about 10 to 4000 J / m 2 (wavelength 365 nm exposure dose conversion) is desired. Irradiate through or without the mask.
  • the exposure light source is not limited, and ultraviolet rays such as i-line, g-line, and h-line, KrF (wavelength 248 nm) laser, ArF (wavelength 193 nm) laser, or the like can be used.
  • post-exposure baking may be performed in which the film is heated in a range of 150 to 450 ° C. for about 1 hour with a heating device such as a hot plate or an oven.
  • the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention preferably have an exposure sensitivity of 100 to 4000 J / m 2 by PLA using a high-pressure mercury lamp as a light source.
  • the sensitivity in patterning exposure using PLA is obtained, for example, by the following method.
  • the composition is spin-coated on a silicon wafer at an arbitrary number of revolutions using a spin coater, and prebaked at 120 ° C. for 2 minutes using a hot plate to produce a film having a thickness of 2 ⁇ m.
  • the prepared film was exposed using PLA (PLA-501F; manufactured by Canon Inc.) through an ultra-high pressure mercury lamp through a gray scale mask for sensitivity measurement, and then developed automatically (AD-2000; Takizawa Sangyo Co., Ltd.). )) And paddle development with a 0.4 wt% tetramethylammonium hydroxide aqueous solution for an arbitrary period of time, followed by rinsing with water for 30 seconds.
  • an exposure amount for resolving a 30 ⁇ m line-and-space pattern with a one-to-one width is obtained as sensitivity.
  • a developing method it is preferable to immerse in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping or paddle.
  • a known alkali developer can be used.
  • known alkali developers include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, and borates, and amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine.
  • an aqueous solution containing one or more quaternary ammonium salts such as tetramethylammonium hydroxide or choline can be used.
  • this film is thermally cured at 120 to 280 ° C. for about 1 hour with a heating device such as a hot plate or oven to obtain a cured film.
  • the cured film obtained from the (I) negative photosensitive resin composition and (II) positive photosensitive resin composition of the present invention is not particularly limited, but 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.
  • the transmittance refers to the transmittance at a wavelength of 400 nm. The hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.
  • the cured film obtained by curing the negative photosensitive resin composition (I) and the positive photosensitive resin composition (II) of the present invention includes a protective film for a touch panel, various hard coat materials, a planarizing film for TFT, It can be used for various protective films such as overcoats for color filters, antireflection films, passivation films, optical filters, insulating films for touch panels, insulating films for TFTs, or photo spacers for color filters.
  • the negative photosensitive resin composition (I) has high hardness, transparency, and heat resistance, and thus can be suitably used as a protective film for a touch panel.
  • Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type.
  • the cured film of this invention can be used suitably.
  • the positive photosensitive resin composition can be processed with high definition and has high adhesiveness, it can be suitably used for a planarization film for TFT (organic passivation film).
  • Synthesis Example 1 Synthesis of Silane Coupling Agent (A1) A 200 mL flask was charged with 20 g of triethoxysilylpropyl isocyanate and 80 g of glycidol and stirred at 40 ° C. for 12 hours. After confirming the disappearance of the peak of triethoxysilylpropyl isocyanate, which is a raw material, and the appearance of a product peak by gas chromatography, glycidol is removed by a rotary evaporator and a vacuum pump with a trap to obtain a silane coupling agent (A1). It was.
  • Synthesis Example 2 Synthesis of Silane Coupling Agent (A2) A silane coupling agent (A2) was obtained in the same manner as in Synthesis Example 1 except that glycidol was changed to 2-ethyloxetanylmethanol.
  • Synthesis Example 3 Synthesis of Silane Coupling Agent (A3) A silane coupling agent (A3) was obtained in the same manner as in Synthesis Example 1 except that glycidol was changed to tetrahydrofurfuryl alcohol.
  • Synthesis Example 4 Synthesis of Silane Coupling Agent (A4) The same procedure as in Synthesis Example 1 was conducted except that glycidol was changed to furfuryl alcohol to obtain a silane coupling agent (A4).
  • Synthesis Example 5 Synthesis of Silane Coupling Agent (A5) A silane coupling agent (A5) was obtained in the same manner as in Synthesis Example 1 except that glycidol was changed to thienylmethanol.
  • Synthesis Example 6 Synthesis of Silane Coupling Agent (A6) A silane coupling agent (A6) was obtained in the same manner as in Synthesis Example 1 except that glycidol was changed to 1-methyl-2-pyrrolidinemethanol.
  • Synthesis Example 7 Synthesis of Silane Coupling Agent (A7) A 200 mL flask was charged with 20 g of 2-((3-triethoxysilylpropyl) amino) ethyl isocyanate and 80 g of tetrahydrofurfuryl alcohol and stirred at 40 ° C. for 12 hours. After confirming the disappearance of the peak of triethoxysilylpropyl isocyanate, which is a raw material, and the appearance of a product peak by gas chromatography, tetrahydrofurfuryl alcohol was removed by a rotary evaporator and a vacuum pump with a trap, and a silane coupling agent (A7 )
  • Synthesis Example 8 Synthesis of Polysiloxane Solution (B1) In a 500 mL flask, 40.86 g (0.3 mol) of methyltrimethoxysilyl, 69.41 g (0.35 mol) of phenyltrimethoxysilane, and ⁇ -acryloylpropyltrimethoxysilane 82. 04 g (0.35 mol) and 192.3 g of DAA (diacetone alcohol) were charged, immersed in an oil bath at 40 ° C. and stirred, with 54.0 g of water (theoretical amount required for hydrolysis) added with 0.39 g of phosphoric acid (theoretical amount required for hydrolysis).
  • DAA diacetone alcohol
  • DAA was added to the obtained DAA solution of polysiloxane so that the polymer concentration was 40 wt% to obtain a polysiloxane solution (B1). In addition, it was 4500 (polystyrene conversion) when the weight average molecular weight (Mw) of the obtained polymer was measured by GPC.
  • MTM methyltrimethoxysilane
  • PTM phenyltrimethoxysilane
  • ETM 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane
  • NphTM 1-naphthyltrimethoxysilane
  • TEOS tetraethoxysilane
  • AcrTM ⁇ -acryloylpropyltrimethoxysilane
  • SuTM 3-trimethoxysilylpropyl succinic anhydride
  • polyester resin solution (B9) 148 g of 1,1-bis (4- (2,3-epoxypropyloxy) phenyl) -3-phenylindane, 47 g of acrylic acid, 1 g of tetrabutylammonium acetate ( Hereinafter, “TBAA”), 2.0 g of tert-butylcatechol and 244 g of PGMEA were charged and stirred at 120 ° C. for 5 hours. After cooling to room temperature, 71 g of biphenyltetracarboxylic dianhydride and 1 g of TBAA were added and stirred at 110 ° C. for 3 hours.
  • TBAA tetrabutylammonium acetate
  • Examples 1-7 For the silane coupling agents (A1) to (A7) synthesized in Synthesis Examples 1 to 7, a 10% weight loss temperature was measured using a thermogravimetric analyzer under the following conditions. The calculation was carried out with the weight after holding at 130 ° C. for 30 minutes as 100%. Equipment: TGA-50 (manufactured by Shimadzu Corporation) Conditions: Hold at 130 ° C. for 30 minutes ⁇ Temperature rise (10 ° C./min) ⁇ 500° C. Atmosphere: 20 mL / min under air Comparative Example 1 The silane coupling agent (A8) synthesized in Comparative Synthesis Example 1 was evaluated for heat resistance by thermogravimetric analysis in the same manner as in Example 1. The results of Examples 1 to 7 and Comparative Example 1 are shown in Table 3.
  • Example 8 Under a yellow light, 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure OXE-01; manufactured by BASF) 0.278 g, hydroquinone methyl ether (HQME) 0 0.017 g and 0.166 g of the silane coupling agent (A1) were dissolved in 2.846 g of DAA (diacetone alcohol) and 4.033 g of PGMEA, and a silicone surfactant BYK-333 (manufactured by Big Chemie Japan Co., Ltd.) 0.2000 g of PGMEA 1 wt% solution (corresponding to a concentration of 100 ppm) was added and stirred.
  • DAA diacetone alcohol
  • PGMEA silicone surfactant BYK-333
  • a glass substrate on which an ITO thin film is applied (hereinafter referred to as “ITO substrate”), or a glass substrate on which a molybdenum / aluminum / molybdenum (MAM) laminated thin film or a silicon nitride thin film (SiNx) is applied (hereinafter referred to as “ MAM substrate "or” SiNx substrate ”) was used.
  • ITO substrate glass substrate on which an ITO thin film is applied
  • MAM substrate "or” SiNx substrate a glass substrate on which a molybdenum / aluminum / molybdenum (MAM) laminated thin film or a silicon nitride thin film (SiNx) is applied
  • the resolution was measured by the minimum pattern size after development at the optimum exposure amount.
  • the development adhesiveness was evaluated based on the minimum pattern size at which the remaining pattern did not peel off after development at the optimum exposure amount.
  • the film thickness was measured at a refractive index of 1.55 using Lambda Ace STM-602 (Dainippon Screen Mfg. Co., Ltd.). However, it was measured at a refractive index of 1.65 only when (F) metal oxide particles were used.
  • the photosensitive resin composition was spin-coated on a 5 cm square Tempax glass substrate (manufactured by AGC Techno Glass Co., Ltd.) using a spin coater, and then at 90 ° C. using a hot plate. Prebaking was performed for 2 minutes to prepare a prebaked film having a thickness of 1.8 ⁇ m.
  • the photosensitive resin composition used was (I) a negative photosensitive resin composition
  • the obtained pre-baked film was exposed to 2000 J / m 2 on the whole surface with an ultrahigh pressure mercury lamp, and 2.38 wt% using an automatic developing device.
  • it was shower-developed with 0.4 wt% TMAH aqueous solution for 90 seconds and then rinsed with water for 30 seconds.
  • the pre-baked film is subjected to shower development with a 2.38 wt% or 0.4 wt% TMAH aqueous solution for 90 seconds using an automatic developing device, and then water Then, the entire surface was exposed to 2000 J / m 2 with an ultra high pressure mercury lamp. Finally, an oven (“IHPS-222” manufactured by ESPEC Corporation) was cured in air at 230 ° C. for 1 hour to prepare a cured film having a thickness of 1.5 ⁇ m.
  • UV-260 ultraviolet-visible spectrophotometer
  • Adhesive evaluation A cured film having a thickness of 1.5 ⁇ m is formed on an ITO substrate, MAM substrate, or SiNx substrate in the same manner as described in (2) above, and JIS “K5600-5-6” is used.
  • Example 36 A touch panel member was produced according to the following procedure.
  • the resulting film was exposed to a pattern using an ultra-high pressure mercury lamp through a mask using PLA, then shower-developed with a 2.38 wt% TMAH aqueous solution for 90 seconds using an automatic developing device, and then rinsed with water for 30 seconds. Thereafter, the ITO is etched by immersing in a 3.5% oxalic acid aqueous solution for 150 seconds, and the photoresist is removed by treatment with a stripping solution (N-321; manufactured by Nagase ChemteX Corp.) at 50 ° C. for 120 seconds. An annealing treatment was performed at 230 ° C. for 30 minutes to produce a glass substrate having ITO (reference numeral 2 in FIGS. 1 and 2) with a film thickness of 150 nm (corresponding to a in FIG. 1).
  • a MAM wiring (reference numeral 4 in FIGS. 1 and 2) was produced by the same procedure as in (1) except that the mixed solution was used (corresponding to c in FIG. 1). The thickness of the MAM was adjusted to 250 nm.
  • Tables 7 and 8 show the evaluation results of Examples 8 to 35 and Comparative Examples 2 to 5.
  • the cured films obtained from the resin compositions obtained in Examples 8 to 35 all have an excellent patterned structure, transparency and adhesiveness.
  • insulating films and protective films for touch panels, flat TFTs It had the characteristics required for the chemical conversion film and the CF overcoat.
  • the cured film obtained by curing the negative photosensitive resin composition and the positive photosensitive resin composition containing the silane coupling agent of the present invention includes a touch sensor in addition to various hard coat films such as a protective film for a touch panel. It is suitably used for insulating films for TFTs, flattening films for TFTs of liquid crystal or organic EL displays, metal wiring protective films, insulating films, antireflection films, antireflection films, optical filters, overcoats for color filters, pillar materials, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Photolithography (AREA)

Abstract

La présente invention concerne un agent de couplage au silane qui possède un bon effet améliorant le décollement et le flottage d'un motif au moment du développement, un bon effet améliorant l'adhésivité à des substrats de base après un traitement de durcissement à chaud ou un traitement chimique, est résistant à la chaleur et ne requiert pas de composés toxiques préoccupants pendant la synthèse. Cet agent de couplage au silane est caractérisé en qu'il est représenté par une formule structurale spécifique comportant un groupe organique univalent en C1-30 qui possède une structure hétérocyclique.
PCT/JP2013/056073 2012-03-30 2013-03-06 Agent de couplage au silane, composition de résine photosensible, film durci et élément d'écran tactile WO2013146130A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2012-079381 2012-03-30
JP2012079381 2012-03-30

Publications (1)

Publication Number Publication Date
WO2013146130A1 true WO2013146130A1 (fr) 2013-10-03

Family

ID=49259401

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2013/056073 WO2013146130A1 (fr) 2012-03-30 2013-03-06 Agent de couplage au silane, composition de résine photosensible, film durci et élément d'écran tactile

Country Status (3)

Country Link
JP (1) JPWO2013146130A1 (fr)
TW (1) TWI560194B (fr)
WO (1) WO2013146130A1 (fr)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015125190A (ja) * 2013-12-25 2015-07-06 東京応化工業株式会社 感光性樹脂組成物
JP2015127803A (ja) * 2013-11-29 2015-07-09 東レ株式会社 感光性樹脂組成物、それを硬化させてなる硬化膜ならびにそれを具備する発光素子および固体撮像素子
CN104932198A (zh) * 2014-03-17 2015-09-23 奇美实业股份有限公司 感光性树脂组合物及其应用
JP2015184575A (ja) * 2014-03-25 2015-10-22 株式会社日本触媒 アルカリ可溶性樹脂を含むレジスト組成物及びその保存方法
JP2015218139A (ja) * 2014-05-19 2015-12-07 株式会社Kri ケイ素系化合物
JPWO2013187209A1 (ja) * 2012-06-12 2016-02-04 株式会社Adeka 感光性組成物
CN105467761A (zh) * 2014-09-30 2016-04-06 新日铁住金化学株式会社 触摸屏用感光性树脂组合物及其硬化膜、以及具有该硬化膜的触摸屏
JP2016186047A (ja) * 2015-03-27 2016-10-27 味の素株式会社 分子接合剤
JP2017008246A (ja) * 2015-06-24 2017-01-12 東京応化工業株式会社 組成物
WO2019028013A1 (fr) * 2017-07-31 2019-02-07 Dow Silicones Corporation Composition de résine doublement durcissable, corps durci préparé à partir de celle-ci, et dispositif électronique comprenant un tel corps durci
JP2019178092A (ja) * 2018-03-30 2019-10-17 株式会社松風 エポキシ環とウレタン基を有するシランカップリング化合物およびそれらを含有する医科歯科模型用硬化性組成物
WO2021018926A1 (fr) * 2019-07-31 2021-02-04 Merck Patent Gmbh Composition photosensible de type négatif
TWI722039B (zh) * 2015-11-25 2021-03-21 南韓商羅門哈斯電子材料韓國公司 感光性樹脂組合物及自其製備之固化膜

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
TWI566037B (zh) * 2015-04-17 2017-01-11 奇美實業股份有限公司 感光性樹脂組成物及其應用
TWI646391B (zh) * 2015-12-24 2019-01-01 奇美實業股份有限公司 黑色矩陣用之感光性樹脂組成物及其應用
JP6917815B2 (ja) * 2017-07-19 2021-08-11 株式会社ニコン 化合物、パターン形成用基板、カップリング剤及びパターン形成方法
WO2019189387A1 (fr) * 2018-03-30 2019-10-03 東レ株式会社 Composition de résine photosensible de type positif, film durci de cette dernière et élément d'imagerie à semi-conducteurs doté de cette dernière

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330485A (ja) * 1997-03-25 1998-12-15 Ivoclar Ag 加水分解可能でかつ重合可能なオキセタンシラン
JP2001329112A (ja) * 2000-05-23 2001-11-27 Toray Ind Inc シランカップリング剤、硬化性樹脂溶液組成物、及びそれからなる機能性硬化物
JP2004127583A (ja) * 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 有機−無機ハイブリッド型プロトン伝導材料及び燃料電池
WO2009096050A1 (fr) * 2008-01-28 2009-08-06 Toray Industries, Inc. Compositions de résine siloxane
JP2010520952A (ja) * 2007-03-09 2010-06-17 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド エポキシシラン、その製造プロセス、およびそれを含有する硬化性組成物
JP2010163633A (ja) * 2009-01-13 2010-07-29 Shin-Etsu Chemical Co Ltd 金属表面処理剤、表面処理鋼材及びその表面処理方法、並びに塗装鋼材及びその製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6096903A (en) * 1997-03-25 2000-08-01 Ivoclar Ag Hydrolysable and polymerizable oxetane silanes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10330485A (ja) * 1997-03-25 1998-12-15 Ivoclar Ag 加水分解可能でかつ重合可能なオキセタンシラン
JP2001329112A (ja) * 2000-05-23 2001-11-27 Toray Ind Inc シランカップリング剤、硬化性樹脂溶液組成物、及びそれからなる機能性硬化物
JP2004127583A (ja) * 2002-09-30 2004-04-22 Fuji Photo Film Co Ltd 有機−無機ハイブリッド型プロトン伝導材料及び燃料電池
JP2010520952A (ja) * 2007-03-09 2010-06-17 モメンティブ パフォーマンス マテリアルズ インコーポレイテッド エポキシシラン、その製造プロセス、およびそれを含有する硬化性組成物
WO2009096050A1 (fr) * 2008-01-28 2009-08-06 Toray Industries, Inc. Compositions de résine siloxane
JP2010163633A (ja) * 2009-01-13 2010-07-29 Shin-Etsu Chemical Co Ltd 金属表面処理剤、表面処理鋼材及びその表面処理方法、並びに塗装鋼材及びその製造方法

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2013187209A1 (ja) * 2012-06-12 2016-02-04 株式会社Adeka 感光性組成物
JP2015127803A (ja) * 2013-11-29 2015-07-09 東レ株式会社 感光性樹脂組成物、それを硬化させてなる硬化膜ならびにそれを具備する発光素子および固体撮像素子
JP2015125190A (ja) * 2013-12-25 2015-07-06 東京応化工業株式会社 感光性樹脂組成物
CN104932198A (zh) * 2014-03-17 2015-09-23 奇美实业股份有限公司 感光性树脂组合物及其应用
JP2015184575A (ja) * 2014-03-25 2015-10-22 株式会社日本触媒 アルカリ可溶性樹脂を含むレジスト組成物及びその保存方法
JP2015218139A (ja) * 2014-05-19 2015-12-07 株式会社Kri ケイ素系化合物
CN105467761A (zh) * 2014-09-30 2016-04-06 新日铁住金化学株式会社 触摸屏用感光性树脂组合物及其硬化膜、以及具有该硬化膜的触摸屏
KR20160038797A (ko) * 2014-09-30 2016-04-07 신닛테츠 수미킨 가가쿠 가부시키가이샤 터치 패널용 감광성 수지 조성물 및 그 경화막, 그리고 당해 경화막을 갖는 터치 패널
JP2016071359A (ja) * 2014-09-30 2016-05-09 新日鉄住金化学株式会社 タッチパネル用感光性樹脂組成物およびその硬化膜、ならびに当該硬化膜を有するタッチパネル
TWI696888B (zh) * 2014-09-30 2020-06-21 日商日鐵化學材料股份有限公司 觸控面板用感光性樹脂組合物及其硬化膜、以及具有該硬化膜的觸控面板
CN105467761B (zh) * 2014-09-30 2020-11-06 日铁化学材料株式会社 触摸屏用感光性树脂组合物及其硬化膜、以及具有该硬化膜的触摸屏
CN112162462A (zh) * 2014-09-30 2021-01-01 日铁化学材料株式会社 触摸屏用感光性树脂组合物及其硬化膜、以及具有该硬化膜的触摸屏
KR102470292B1 (ko) * 2014-09-30 2022-11-23 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 터치 패널용 감광성 수지 조성물 및 그 경화막, 그리고 당해 경화막을 갖는 터치 패널
JP2016186047A (ja) * 2015-03-27 2016-10-27 味の素株式会社 分子接合剤
JP2017008246A (ja) * 2015-06-24 2017-01-12 東京応化工業株式会社 組成物
TWI722039B (zh) * 2015-11-25 2021-03-21 南韓商羅門哈斯電子材料韓國公司 感光性樹脂組合物及自其製備之固化膜
WO2019028013A1 (fr) * 2017-07-31 2019-02-07 Dow Silicones Corporation Composition de résine doublement durcissable, corps durci préparé à partir de celle-ci, et dispositif électronique comprenant un tel corps durci
US11390748B2 (en) 2017-07-31 2022-07-19 Dow Silicones Corporation Dually-curable resin composition, cured body prepared therefrom, and electronic device comprising such cured body
JP2019178092A (ja) * 2018-03-30 2019-10-17 株式会社松風 エポキシ環とウレタン基を有するシランカップリング化合物およびそれらを含有する医科歯科模型用硬化性組成物
JP7104489B2 (ja) 2018-03-30 2022-07-21 株式会社松風 エポキシ環とウレタン基を有するシランカップリング化合物およびそれらを含有する医科歯科模型用硬化性組成物
KR20220042177A (ko) * 2019-07-31 2022-04-04 메르크 파텐트 게엠베하 네거티브형 감광성 조성물
WO2021018926A1 (fr) * 2019-07-31 2021-02-04 Merck Patent Gmbh Composition photosensible de type négatif
US11579530B2 (en) 2019-07-31 2023-02-14 Merck Patent Gmbh Negative type photosensitive composition
KR102539233B1 (ko) 2019-07-31 2023-06-05 메르크 파텐트 게엠베하 네거티브형 감광성 조성물

Also Published As

Publication number Publication date
TWI560194B (en) 2016-12-01
JPWO2013146130A1 (ja) 2015-12-10
TW201404781A (zh) 2014-02-01

Similar Documents

Publication Publication Date Title
WO2013146130A1 (fr) Agent de couplage au silane, composition de résine photosensible, film durci et élément d'écran tactile
JP5212571B2 (ja) タッチパネル部材
JP5589387B2 (ja) シロキサン樹脂組成物およびそれを用いたタッチパネル用保護膜
US10431753B2 (en) Substrate for display, color filter using the same and method for the production thereof, organic EL element and method for the production thereof, and flexible organic EL display
KR102341566B1 (ko) 감광성 수지 조성물, 경화막, 적층체, 터치 패널용 부재, 및 경화막의 제조 방법
JP6417669B2 (ja) 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の製造方法
JP5459315B2 (ja) シランカップリング剤、ネガ型感光性樹脂組成物、硬化膜、およびタッチパネル用部材
JP6323007B2 (ja) 感光性樹脂組成物、導電性配線保護膜及びタッチパネル部材
JP5407210B2 (ja) シロキサン樹脂組成物およびそれを用いた硬化膜
JP5671936B2 (ja) ネガ型感光性樹脂組成物およびそれを用いた硬化膜
WO2011129312A1 (fr) Composition de résine photosensible pour négatif, pellicule traitée thermiquement, et élément pour panneau tactile
JP5327345B2 (ja) ネガ型感光性樹脂組成物、硬化膜、およびタッチパネル用部材。
JP2016072246A (ja) ディスプレイ用支持基板、それを用いたカラーフィルターおよびその製造方法、有機ｅｌ素子およびその製造方法、ならびにフレキシブル有機ｅｌディスプレイ
WO2013147028A1 (fr) Composition de résine, film transparent pour capteurs d'écran tactile l'utilisant, et écran tactile
JP7119390B2 (ja) ネガ型感光性樹脂組成物およびそれを用いた硬化膜
JP2018120069A (ja) ネガ型感光性樹脂組成物、硬化膜およびタッチパネル部材
JP2022064302A (ja) ネガ型シロキサン樹脂組成物、硬化膜および素子

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2013514477

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13769052

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 13769052

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE