WO2019102655A1 - Composition de résine de siloxane, film durci et dispositif d'affichage - Google Patents

Composition de résine de siloxane, film durci et dispositif d'affichage Download PDF

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Publication number
WO2019102655A1
WO2019102655A1 PCT/JP2018/029343 JP2018029343W WO2019102655A1 WO 2019102655 A1 WO2019102655 A1 WO 2019102655A1 JP 2018029343 W JP2018029343 W JP 2018029343W WO 2019102655 A1 WO2019102655 A1 WO 2019102655A1
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Prior art keywords
group
resin composition
siloxane resin
polysiloxane
mol
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PCT/JP2018/029343
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English (en)
Japanese (ja)
Inventor
飯塚英祐
諏訪充史
小林秀行
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東レ株式会社
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Priority to CN201880075015.0A priority Critical patent/CN111373325B/zh
Priority to JP2018541436A priority patent/JP7172598B2/ja
Priority to KR1020207004247A priority patent/KR20200079231A/ko
Publication of WO2019102655A1 publication Critical patent/WO2019102655A1/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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • 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
    • G—PHYSICS
    • G06—COMPUTING; CALCULATING OR COUNTING
    • G06F—ELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means

Definitions

  • the present invention relates to a siloxane resin composition, a cured film and a display device.
  • a touch sensor used for a capacitive touch panel has a wiring in which ITO (Indium Tin Oxide) or metal (silver, molybdenum, aluminum, etc.) is patterned on glass, and an insulating film or wiring is formed at the intersection of the wirings.
  • ITO Indium Tin Oxide
  • metal silver, molybdenum, aluminum, etc.
  • a structure having a protective film that protects the In addition to transparency, the insulating film formed at the intersection of the wiring is used for fine pattern processability, adhesion to a glass substrate to be a base substrate and adhesion to a metal substrate such as a conductive film, and conductive film pattern formation Chemical resistance to etchant solution and alkaline stripping solution is required.
  • a resin composition capable of forming a transparent film excellent in heat resistance and chemical resistance it has a developable group, and a developable polysiloxane substantially free of a radically polymerizable group, and a radically polymerizable group.
  • Resin composition having two types of polysiloxane of polymerizable polysiloxane substantially having no developable group and having a polyfunctional monomer and a polyfunctional cyclic ether compound having two or more cyclic ether structures A thing is proposed (for example, refer to patent documents 2).
  • the present invention provides a siloxane resin composition which is excellent in storage stability and which can obtain a cured film excellent in adhesion to a glass substrate or metal substrate and chemical resistance even under low temperature curing conditions of 100 ° C. or less.
  • the purpose is to
  • the present invention is a siloxane resin composition containing (A) polysiloxane, (B) photosensitizer, (C) polymerizable compound having a phosphorus atom, and (D) a silane compound having a ureido group.
  • the siloxane resin composition of the present invention is excellent in storage stability. According to the siloxane resin composition of the present invention, a cured film excellent in adhesion to a glass substrate or a metal substrate and chemical resistance can be obtained even under low temperature curing conditions of 100 ° C. or less.
  • the siloxane resin composition of the present invention comprises (A) polysiloxane, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, and (D) a silane compound having a ureido group.
  • the siloxane resin composition of the present invention is a negative photosensitive resin composition
  • the polysiloxane has a solubility in an alkali developing solution and functions as a binder resin which can be patterned by photolithography.
  • the siloxane resin composition of the present invention is a positive photosensitive resin composition
  • the (A) polysiloxane imparts high heat resistance and light resistance by condensation at the time of heat curing.
  • the photosensitizer imparts negative or positive photosensitivity, and has an action of enabling fine pattern formation by photolithography.
  • the polymerizable compound having a phosphorus atom (C) can improve the adhesion to a metal substrate and the chemical resistance.
  • the condensation of the (A) polysiloxane proceeds by the acidity of the polymerizing compound having a phosphorus atom (C);
  • the storage stability is improved by combining the polymerizable compound having a phosphorus atom (C) and the silane compound having a ureido group (D) which is a weakly basic substance. Play an effect.
  • the silane compound which has (D) ureido group has an effect of improving adhesiveness with a metal substrate and a glass substrate, and chemical resistance.
  • (A) Polysiloxane refers to a polymer having a siloxane bond in the main chain skeleton and having a weight average molecular weight (Mw) of 1,000 or more.
  • Mw of (A) polysiloxane refers to the polystyrene conversion value measured by gel per emission chromatography (GPC).
  • GPC gel per emission chromatography
  • the Mw of the (A) polysiloxane is more preferably 2,000 or more.
  • the Mw of the (A) polysiloxane is preferably 100,000 or less, more preferably 50,000 or less.
  • polysiloxane has (a1) cationically polymerizable group, (a2) radically polymerizable group and (a3) alkali-soluble group Is preferred.
  • A1 By having a cationically polymerizable group, curing can be performed at a lower temperature, and hardness can be improved under a low temperature curing condition of 100 ° C. or less. Moreover, since permeation of a chemical
  • (A2) By having a radically polymerizable group, the contrast of the degree of curing between the exposed area and the unexposed area can be easily obtained, so that the generation of development residues can be suppressed, and a higher definition pattern can be obtained. Moreover, photocurability can be improved by having a radically polymerizable group (a2), and hardness can be improved under low temperature curing conditions of 100 ° C. or less. Moreover, since permeation of a chemical
  • (a3) by having an alkali-soluble group, (a3) the alkali-soluble group acts as an acidic catalyst, and (A) the condensation of the polysiloxane proceeds, so the hardness is improved under low temperature curing conditions of 100 ° C or less. Can. Furthermore, the chemical resistance can be further improved by the improvement of the crosslink density of the cured film.
  • the content of the (a1) cationically polymerizable group is 1 to 30% by mole based on 100% by mole of the total content of (a1) cationically polymerizable group, (a2) radically polymerizable group and (a3) alkali-soluble group. preferable.
  • (A1) By setting the content of the cationically polymerizable group to 1 mol% or more, the crosslinking reaction by cationic polymerization can be more effectively progressed, and the hardness and chemical resistance of the cured film can be further improved.
  • the content of the cationically polymerizable group (a1) is more preferably 5 mol% or more.
  • the content of the (a1) cationically polymerizable group is 30 mol% or less, the hydrophilicity of the cured film can be appropriately suppressed, and the hardness and the chemical resistance can be further improved.
  • the content of the cationically polymerizable group (a1) is more preferably 20 mol% or less.
  • the content of the (a2) radically polymerizable group is 50 to 90 mol based on 100 mol% of the total content of the (a1) cationically polymerizable group, the (a2) radically polymerizable group and the (a3) alkali-soluble group. % Is preferred.
  • the crosslinking reaction by radical polymerization can be sufficiently advanced, and the hardness and the chemical resistance can be further improved. Further, by setting the content of the (a2) radically polymerizable group to 50 mol% or more, the contrast of the curing degree of the exposed portion and the unexposed portion can be easily obtained, and thus a higher definition pattern can be obtained. On the other hand, by setting the content of the (a2) radically polymerizable group to 90 mol% or less, a higher definition pattern can be obtained.
  • the content of the radically polymerizable group (a2) is more preferably 85 mol% or less.
  • the content of the group can be calculated by 29 Si-NMR.
  • a solution in which polysiloxane is mixed with hexamethylcyclotrisiloxane which is a standard substance is subjected to a 29 Si-NMR measurement apparatus (for example, AVANCE 400 (manufactured by Bruker)) at a room temperature (about 22 ° C.) by DD / MAS method.
  • the 29 Si-NMR measurement is carried out in accordance with the above, and the content of each group is calculated from the peak integral ratio.
  • the measurement nuclear frequency is 79.4948544 MHz ( 29 Si nucleus)
  • the spectrum width is 40 kHz
  • the pulse width is 4.2 ⁇ sec (90 ° pulse).
  • the polysiloxane having (a1) cationically polymerizable group, (a2) radically polymerizable group and (a3) alkali soluble group is an organosilane compound having cationically polymerizable group, an organosilane compound containing radically polymerizable group, alkali solubility It can be obtained by hydrolyzing and polycondensing organosilane compounds having a group and, if necessary, other organosilane compounds.
  • Examples of the cationically polymerizable group (a1) include an epoxy group, an oxetanyl group, and a vinyl ether group. Among these, an epoxy group and an oxetanyl group are preferable, and the chemical resistance and hardness of the cured film under low temperature curing conditions can be further improved.
  • organosilane compounds having a cationically polymerizable group examples include glycidoxymethyltrimethoxysilane, glycidoxymethyltriethoxysilane, ⁇ -glycidoxyethyltrimethoxysilane, and ⁇ -glycidoxyethyltrimethoxysilane.
  • Two or more of these may be used.
  • Examples of the radically polymerizable group (a2) include vinyl group, ⁇ -methylvinyl group, allyl group, styryl group, (meth) acryloyl group and the like.
  • a styryl group having high hydrophobicity and heat reactivity, and a (meth) acryloyl group having high light reactivity are preferable, and the chemical resistance and hardness of the cured film can be further improved. It is more preferable to use both a styryl group and a (meth) acryloyl group.
  • organosilane compounds having a radically polymerizable group examples include organosilane compounds having a vinyl group such as vinyltrimethoxysilane, vinyltriethoxysilane and vinyltri (methoxyethoxy) silanesilane; vinylmethyldimethoxysilane, vinyl Organosilane compounds having an ⁇ -methylvinyl group such as methyldiethoxysilane and vinylmethyldi (methoxyethoxy) silane; allyltrimethoxysilane, allyltriethoxysilane, allyltri (methoxyethoxy) silane, allylmethyldimethoxysilane, allylmethyldiethoxy Organosilane compounds having an allyl group such as silane, allylmethyldi (methoxyethoxy) silane; styryltrimethoxysilane, styryltriethoxysilane, styrylto Organosilane compounds having a s
  • Examples of the (a3) alkali-soluble group include a carboxylic acid group and a carboxylic acid anhydride group. Among these, a carboxylic anhydride group is more preferable.
  • Organosilane compounds having an alkali-soluble group for example, 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-triphenoxysilylpropylsuccinic anhydride, 3-trimethoxy Organosilane compounds having a carboxylic acid anhydride group such as silylpropyl cyclohexyl dicarboxylic acid anhydride, 3-trimethoxysilyl propyl phthalic acid anhydride and the like can be mentioned. Two or more of these may be used. Among these, 3-trimethoxysilylpropylsuccinic anhydride and 3-triethoxysilylpropylsuccinic anhydride are preferable from the viewpoint of developability.
  • organosilane compounds for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri (methoxyethoxy) silane, methyltripropoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane Ethoxysilane, hexyltrimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2 aminoethyl) -3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxy
  • the polysiloxane (A) can be obtained by hydrolyzing the organosilane compound and subjecting the obtained hydrolyzate to a condensation reaction in the presence or absence of a solvent.
  • a catalyst such as an acid catalyst or a base catalyst may be used.
  • a base catalyst is preferable, and a basic aqueous solution using diisobutylamine, diazabicycloundecene, dicyclohexylamine or the like is more preferable.
  • the content of the catalyst is preferably 0.1 parts by weight or more and 5 parts by weight or less with respect to 100 parts by weight of all the alkoxysilane compounds used for the hydrolysis reaction.
  • the total amount of the alkoxysilane compound refers to the total amount of the alkoxysilane compound, its hydrolyzate and its condensate, and hereinafter the same.
  • a solvent used for the hydrolysis reaction diacetone alcohol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol mono-t-butyl ether, ⁇ -Butyrolactone etc. are preferred. Two or more of these may be used.
  • the content of the solvent is preferably 80 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the total alkoxysilane compound.
  • a solvent is generated by the hydrolysis reaction
  • the whole or a part of the resulting alcohol or the like may be distilled and removed by heating and / or under reduced pressure, and then a suitable solvent may be added.
  • ion exchange water As water used for a hydrolysis reaction, ion exchange water is preferable.
  • the amount of water is preferably 1.0 to 4.0 moles relative to 1 mole of the alkoxysilane compound.
  • the heating temperature in the condensation reaction is preferably 100 to 110.degree.
  • the condensation reaction is preferably carried out while distilling off water and alcohol produced by hydrolysis and condensation reaction out of the reaction system.
  • the above-mentioned catalyst is not contained in the polysiloxane solution after the hydrolysis and condensation reaction, and the catalyst can be removed if necessary.
  • the removal method water washing and / or treatment of ion exchange resin is preferable.
  • the water washing is a method of diluting the polysiloxane solution with a suitable hydrophobic solvent and then washing with water several times to concentrate the obtained organic layer with an evaporator or the like.
  • Treatment with an ion exchange resin is a method in which a polysiloxane solution is brought into contact with a suitable ion exchange resin.
  • the content of (A) polysiloxane in the siloxane resin composition of the present invention is preferably 10 to 80% by weight. Moreover, 10 weight% or more in solid content is preferable, and, as for content of (A) polysiloxane in a siloxane resin composition, 20 weight% or more is more preferable. On the other hand, the content of the (A) polysiloxane is preferably 50% by weight or less in the solid content.
  • the photosensitizer imparts negative or positive photosensitivity, and has an action of enabling formation of a fine pattern by photolithography.
  • a photoacid generator is preferably a (b2) quinonediazide compound.
  • a radical polymerization initiator refers to a compound which is decomposed and / or reacted by light (including ultraviolet light and electron beam) or heat to generate a radical.
  • the radical polymerization initiator is preferably a photoradical generator which is decomposed and / or reacted with light (including ultraviolet light and electron beam) to generate a radical. It is more preferable to contain a photoradical generator and a thermal radical generator that generates a radical by being decomposed and / or reacted by heat.
  • Examples of the photo-radical generator include ⁇ -aminoalkylphenone compounds, acyl phosphine oxide compounds, oxime ester compounds, ketone compounds, benzoin compounds, acyl oxime compounds, metallocene compounds, thioxanthone compounds, benzophenone compounds having an amino group, amino groups And benzoate compounds having ketones, ketone compounds, coumarin compounds, anthracene compounds, azo compounds, carbon tetrabromide, tribromophenyl sulfone and the like. Two or more of these may be contained.
  • ⁇ -aminoalkylphenone compounds acyl phosphine oxide compounds, oxime ester compounds, benzophenone compounds having an amino group, and benzoic acid ester compounds having an amino group are preferable.
  • These compounds are also involved in the crosslinking of the siloxane as a base or acid during light irradiation and thermal curing, and therefore the hardness can be further improved.
  • Examples of ⁇ -aminoalkylphenone compounds include 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1-l. (4-morpholin-4-yl-phenyl) -butan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 and the like.
  • acyl phosphine oxide compound for example, 2,4,6-trimethyl benzoyl phenyl phosphine oxide, bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide, bis (2,6-dimethoxy benzoyl)-(2 And 4,4-trimethylpentyl) -phosphine oxide.
  • oxime ester compounds include 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1,2-octanedione, 1- [4- (phenylthio) -2- (o-) Benzoyloxime)], 1-phenyl-1,2-butadione-2- (o-methoxycarbonyl) oxime, 1,3-diphenylpropanetrione-2- (o-ethoxycarbonyl) oxime, ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) and the like.
  • benzophenone compounds having an amino group examples include 4,4-bis (dimethylamino) benzophenone, 4,4-bis (diethylamino) benzophenone and the like.
  • benzoic acid ester compounds having an amino group examples include ethyl p-dimethylaminobenzoate, 2-ethylhexyl-p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate and the like.
  • thermal radical generator for example, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamine], 2,2′-azobis [2-methyl-N- (2-propenyl)] -2-Methylpropionamine], 2,2'-azobis (N-butyl-2-methylpropionamine), dimethyl 2,2'-azobis (isobutyrate), 4,4'-azobis (4-cyanovaleric acid) 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2 ' And -azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-carboxyethyl) 2-methylpropionamidine] n-hydrate and the like. Two or more of these may be contained. Among these, dimethyl 2,2′-azobis (isobutyrate) is preferable from the viewpoint of
  • the content of the (b1) radical polymerization initiator in the siloxane resin composition is preferably 1% by weight or more, and preferably 10% by weight or less in the solid content.
  • the polyfunctional monomer refers to a compound having two or more (meth) acryloyl groups.
  • the double bond equivalent of the polyfunctional monomer is preferably 80 to 400 g / mol from the viewpoint of further improving the sensitivity and hardness.
  • polyfunctional monomers examples include pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol heptaacrylate and tripentaerythritol octata.
  • Acrylate tetrapentaerythritol nonaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol undecaacrylate and the like.
  • dipentaerythritol hexaacrylate is preferable from the viewpoint of improving hardness and chemical resistance.
  • the photoacid generator refers to a compound which causes bond cleavage at the time of exposure to generate an acid, and more specifically, the exposure wavelength 365 nm (i line), 405 nm (h line), 436 nm (g line) or the like It refers to a compound that generates an acid upon irradiation of the mixed line.
  • the quinonediazide compound generates a carboxylic acid group upon exposure, and the exposed area can be dissolved by development.
  • a compound in which a sulfonic acid of naphthoquinone diazide is bound by an ester to a compound having a phenolic hydroxyl group is preferable.
  • BIs-Z As a compound which has a phenolic hydroxyl group used here, BIs-Z, TekP-4HBPA (tetrakis P-DO-BPA), TrIsP-HAP, TrIsP-PA, BIsRS-2P, BIsRS-3P (all, goods, for example) Name, Honshu Chemical Industry Co., Ltd.), BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, manufactured by Asahi Organic Materials Co., Ltd.), 4,4'-sulfonyldiphenol, BPFL (Trade name, manufactured by JFE Chemical Co., Ltd.) and the like.
  • quinone diazide compounds compounds in which 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid is introduced into these compounds having a phenolic hydroxyl group through an ester bond are preferable, for example, THP-17, TDF-517 (trade name, Toyo Synthetic Industry Co., Ltd. product, SBF-525 (trade name, manufactured by AZ Electronic Materials Co., Ltd.) and the like.
  • the siloxane resin composition of the present invention may also contain a photoacid generator other than the (b2) quinonediazide compound.
  • the acid functions as a catalyst that promotes the dehydration condensation of silanols. The presence of the acid at the time of heat curing accelerates the condensation of unreacted silanol groups and increases the degree of crosslinking of the cured film.
  • the siloxane resin composition contains a compound having a cyclic ether group, the acid functions as a polymerization catalyst for the cyclic ether group. The presence of the acid at the time of heat curing accelerates the polymerization of the cyclic ether group and increases the degree of crosslinking of the cured film. By these, the hardness and chemical resistance of a cured film can be improved more.
  • the acid to be generated is preferably a strong acid such as perfluoroalkylsulfonic acid or p-toluenesulfonic acid.
  • Examples of photoacid generators other than quinonediazide compounds include SI-100, SI-101, SI-105, SI-106, SI-109, PI-105, PI-106, PI-109, NAI-. 100, NAI-1002, NAI-1003, NAI-1004, NAI-101, NAI-105, NAI-106, NAI-109, NDI-101, NDI-105, NDI-106, NDI-109, PAI-01, PAI-101, PAI-106, PAI-1001 (all trade names, manufactured by Midori Kagaku Co., Ltd.), SP-077, SP-082 (all trade names, manufactured by ADEKA), TPS-PFBS (goods Name, Toyo Gosei Kogyo Co., Ltd., CGI-MDT, CGI-NIT (all are trade names, manufactured by Chiba Japan Co., Ltd.), W AG-281, WPAG-336, WPAG-339, WPAG-342,
  • the content of the photoacid generator in the siloxane resin composition is preferably 0.5% by weight or more in the solid content, and preferably 25% by weight or less from the viewpoint of improving hardness and chemical resistance, and developing property. .
  • the polymerizable compound having a phosphorus atom comprises a phosphorus atom and a radically polymerizable functional group (radically polymerizable group).
  • radically polymerizable group examples include a vinyl group, an ⁇ -methylvinyl group, an allyl group, a styryl group, a (meth) acryloyl group, a ⁇ - (meth) acryloylethyl group, and a ⁇ - (meth) acryloylpropyl group.
  • (meth) acryloyl group, ⁇ - (meth) acryloylethyl group, and ⁇ - (meth) acryloylpropyl group, which have high light and heat reactivity, are preferable, and the chemical resistance of the cured film can be further improved.
  • the polymerizable compound having a phosphorus atom (C) a compound having a structure represented by the following general formula (1) is preferable.
  • R 1 represents a monovalent organic group having a radical polymerizable group.
  • R 2 represents hydrogen, an alkyl group having 1 to 20 carbon atoms, or a monovalent organic group having a radically polymerizable group.
  • the monovalent organic group having a radically polymerizable group preferably has a hydroxyl group together with the radically polymerizable group.
  • a polymerizable compound having a (C) phosphorus atom is efficiently taken into the (A) polysiloxane, It is possible to suppress bleed out during curing.
  • the monovalent organic group having a radically polymerizable group a ⁇ - (meth) acryloylethyl group and a ⁇ - (meth) acryloylpropyl group are preferable.
  • Examples of the compound having a structure represented by the above general formula (1) include 2-methacryloyloxyethyl acid phosphate (trade name P-1M, manufactured by Kyoeisha Chemical Co., Ltd.), 2-acryloyloxyethyl acid phosphate (Trade name P-1A, manufactured by Kyoeisha Chemical Co., Ltd.), ethylene oxide modified phosphate dimethacrylate (trade name PM-21, manufactured by Nippon Kayaku Co., Ltd.), phosphoric acid-containing epoxy methacrylate (trade name "New Frontier” Phosphoric acid (meth) acrylates such as (registered trademark) S-23A, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd .; vinyl phosphates such as vinylphosphonic acid (trade name: VPA-90, VPA-100, manufactured by BASF) A compound etc. are mentioned. Two or more of these may be contained.
  • content of the polymeric compound which has (C) phosphorus atom in a siloxane resin composition 1 weight% or more in solid content is preferable, and 30 weight% or less is preferable.
  • Silane compound having a ureido group Silane compound having a ureido group
  • a silane compound having a ureido group for example, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-phenylureidopropyltrimethoxysilane, 3- There may be mentioned phenylureidopropyltriethoxysilane, 4-ureidobutyltrimethoxysilane, 4-ureidobutyltriethoxysilane, 4-phenylureidobutyltrimethoxysilane, 4-phenylureidobutyltriethoxysilane and the like.
  • 3-ureidopropyltriethoxysilane and 3-ureidopropyltrimethoxysilane are preferable from the viewpoint of further improving the adhesion to a metal substrate and a glass substrate.
  • the content of the silane compound having a (D) ureido group in the siloxane resin composition is preferably 0.1% by weight or more, and preferably 1% by weight or less in the solid content.
  • the equivalent ratio ((C) / (D)) of the polymerizable compound having a phosphorus atom (C) to the silane compound having a ureido group (D) in the siloxane resin composition of the present invention is a metal substrate and a glass substrate From the viewpoint of further improving the adhesion, 8/2 or more is preferable, and 9/1 or more is more preferable.
  • the equivalent ratio ((C) / (D)) is preferably 9.9 / 0.1 or less, more preferably 9.5 / 0.5 or less, from the viewpoint of storage stability.
  • the equivalent ratio ((C) / (D)) can be calculated from equation (2).
  • the siloxane resin composition of the present invention preferably contains a compound having a cyclic ether group.
  • the cyclic ether group is preferably an epoxy group or an oxetanyl group.
  • the cationic polymerization property is improved, whereby the chemical resistance and the hardness can be further improved.
  • the polysiloxane contains an epoxy group as the (a1) cationically polymerizable group
  • the polysiloxane is (a1) cationically polymerizable group
  • the compound having a cyclic ether group has an epoxy group.
  • an epoxy group and an oxetanyl group coexist in a siloxane resin composition
  • the efficiency of the cationic polymerization of an epoxy group and an oxetanyl group can be improved, and chemical resistance and hardness can be improved more.
  • the content of the compound having a cyclic ether group in the siloxane resin composition is preferably 1% by weight or more, and preferably 20% by weight or less in the solid content.
  • the siloxane resin composition of the present invention may contain other silane compounds in addition to the (D) ureide group-containing silane compound.
  • the organosilane compound illustrated as a raw material of (A) polysiloxane, etc. are mentioned, for example.
  • ⁇ - (meth) acryloylpropyltrimethoxysilane, ⁇ - (meth) acryloylpropyltriethoxysilane, and styryltrimethoxysilane are preferable.
  • the content of the other silane compound in the siloxane resin composition is preferably 1% by weight or more, and preferably 10% by weight or less in the solid content.
  • the siloxane resin composition of the present invention may contain a curing agent.
  • the curing agent include nitrogen-containing organic substances, silicone resin curing agents, various metal alkoxylates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, methylolated urea derivatives and the like. Two or more of these may be contained.
  • metal chelate compounds, methylolated melamine derivatives and methylolated urea derivatives are preferable from the viewpoint of the stability of the curing agent and the processability of the siloxane resin composition.
  • the siloxane resin composition of the present invention may contain a sensitizer as long as the effects of the present invention are not impaired.
  • the sensitivity can be improved by containing a sensitizer.
  • the sensitizer is preferably an anthracene compound from the viewpoint of high sensitivity and suppression of color fading due to light irradiation. 9,10-disubstituted anthracene compounds are more preferable, and 9,10-dialkoxyanthracene compounds are more preferable from the viewpoint of the improvement of the solubility of the sensitizer and the reactivity of the photodimerization reaction.
  • the content of the sensitizer in the siloxane resin composition of the present invention is preferably 0.005 to 5 parts by mass with respect to 100 parts by mass of the (A) polysiloxane.
  • the siloxane resin composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber By containing the ultraviolet absorber, a pattern with higher definition can be formed, and the light resistance of the cured film can be improved. From the viewpoints of transparency and non-coloring property, benzotriazole compounds, benzophenone compounds and triazine compounds are preferable as the ultraviolet absorber.
  • the siloxane resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor include di-t-butylhydroxytoluene, butylhydroxyanisole, hydroquinone, 4-methoxyphenol, 1,4-benzoquinone and t-butyl catechol.
  • IRGANOX registered trademark 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425, 1520, 245, 259, 3114, 565, 295 (trade name, BASF Japan (manufactured by Japan Co., Ltd.) and the like.
  • the siloxane resin composition of the present invention may contain a solvent. Solvents having a boiling point of 250 ° C. or less at atmospheric pressure are preferred. Further, from the viewpoint of suppressing the remaining of the solvent in the cured film, it is preferable to contain 50% by weight or more of the solvent having a boiling point of 150 ° C. or less under atmospheric pressure, based on the entire solvent.
  • Examples of the solvent having a boiling point of 150 ° C. or less at atmospheric pressure include ethanol, isopropanol, 1-propyl alcohol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and the like. Among these, propylene glycol monomethyl ether is preferable from the viewpoint of coatability. Two or more solvents may be contained.
  • the content of the solvent in the siloxane resin composition of the present invention is, for example, generally 50 to 95% by weight when film formation is performed by spin coating.
  • the siloxane resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and a silicone-based surfactant. By containing the surfactant, it is possible to improve the leveling property at the time of application.
  • surfactants for example, “Megafuck” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477, F554, F556, F563 (trade names, Dainippon Ink Chemical Industry Co., Ltd.) Fluorine-based surfactants such as NBX-15, 218 (all trade names, manufactured by Neos Co., Ltd.); “BYK” (registered trademark) 333, 301, 331, 345, 307 (trade names, Big Chemie, Fluorine-based surfactants such as Japan (manufactured by Japan Co., Ltd.); Silicone-based surfactants such as "BYK” 333, 301, 331, 345, 307 (trade names
  • the content of the surfactant in the siloxane resin composition is preferably 0.01% by weight or more in the solid content, and preferably 1.0% by weight or less, from the viewpoint of improving the leveling property at the time of coating.
  • the siloxane resin composition of the present invention may optionally contain additives such as a dissolution inhibitor, a stabilizer, and an antifoaming agent.
  • the typical manufacturing method of the siloxane resin composition of this invention is demonstrated below.
  • the siloxane resin composition of the present invention can be obtained, for example, by mixing the above-mentioned components (A) to (D) and, if necessary, other components. More specifically, for example, (B) a photosensitizer, (C) a polymerizable compound having a phosphorus atom, (D) a silane compound having a ureido group and other additives are added to an optional solvent, and dissolved by stirring. After the addition, (A) the polysiloxane is added, and the method is further stirred for 20 minutes to 3 hours, and the resulting solution is filtered.
  • the cured film of the present invention is obtained by curing the above-mentioned siloxane resin composition.
  • the thickness of the cured film is preferably 0.1 to 15 ⁇ m.
  • the transmittance of the cured film at a wavelength of 400 nm is preferably 85% or more.
  • permeability of a cured film can be adjusted to a desired range with exposure amount and thermosetting temperature.
  • the method for producing a cured film of the present invention will be described by way of examples. After the siloxane resin composition of the present invention is applied onto a base substrate and prebaked, it is preferable to form a negative pattern by exposure and development, and heat cure.
  • Examples of the method of applying the siloxane resin composition include methods such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, and slit coating.
  • the prebaking temperature is preferably 50 to 130 ° C.
  • the prebaking time is preferably 30 seconds to 30 minutes.
  • the film thickness after prebaking is preferably 0.1 to 15 ⁇ m.
  • Examples of the exposure light source include ultraviolet light such as i-line, g-line and h-line, a KrF (wavelength 248 nm) laser, and an ArF (wavelength 193 nm) laser.
  • Examples of the exposure device include a stepper, a mirror projection mask aligner (MPA), a parallel light mask aligner (PLA) and the like.
  • the exposure dose is preferably about 10 to 4000 J / m 2 (in terms of wavelength 365 nm exposure dose). It may be exposed through a desired mask, or may be exposed without a mask.
  • the developing method for example, it is preferable to immerse the exposed pre-baked film in the developer for 5 seconds to 10 minutes by a method such as a shower, dipping or paddle.
  • a developing solution For example, Inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals; Amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine; Tetramethyl
  • alkali compounds such as ammonium hydroxide and quaternary ammonium salts, such as choline etc., etc. are mentioned.
  • After development it is preferable to rinse with water, followed by drying bake at a temperature of 50 to 130 ° C.
  • the heat curing temperature is preferably 60 to 180 ° C.
  • the heat curing time is preferably 15 minutes to 1 hour.
  • the cured film of the present invention includes various protective films such as protective films for touch panels, various hard coating materials, flattening films for TFTs, overcoats for color filters, antireflection films, passivation films, optical filters, insulating films for touch panels, It can be used as an insulating film for TFT, a photo spacer for color filter, and the like.
  • protective films such as protective films for touch panels, various hard coating materials, flattening films for TFTs, overcoats for color filters, antireflection films, passivation films, optical filters, insulating films for touch panels, It can be used as an insulating film for TFT, a photo spacer for color filter, and the like.
  • a protective film for a touch panel an insulating film for a touch panel, and a metal wiring protective film.
  • the touch sensor of the present invention has a transparent electrode, metal wiring, a metal wiring protective film for a touch panel made of the above-described cured film, an insulating film for a touch panel, and the like.
  • the display device of the present invention includes at least one selected from the group consisting of a liquid crystal cell, an organic EL cell, a mini LED cell, and a micro LED cell, a substrate, and the above-described cured film.
  • the mini LED cell refers to a cell in which a large number of LEDs each having a length of about 100 ⁇ m to 10 mm are arranged.
  • the micro LED cell refers to a cell in which a large number of LEDs having a length of less than 100 ⁇ m are arranged.
  • Examples of the display device of the present invention include a liquid crystal display device, an organic EL display device, a mini LED display device, and a micro LED display device.
  • the solid content concentration of the polysiloxane solution in the following synthesis example was determined by the following method. 1.0 g of the polysiloxane solution was weighed into an aluminum cup, and heated at 250 ° C. for 30 minutes using a hot plate to evaporate the liquid. The solid content remaining in the aluminum cup after heating was weighed, and the solid content concentration of the polysiloxane solution was determined from the weight ratio before and after heating.
  • the content of the alkali-soluble group was measured by 29 Si-NMR according to the following method.
  • the polysiloxane is mixed with hexamethylcyclotrisiloxane which is a standard substance, and 29 Si-NMR measurement is performed at room temperature (about 22 ° C.) by the DD / MAS method using AVANCE 400 (manufactured by Bruker), and the peak integration
  • the content of each group was calculated from the ratio.
  • the measurement nuclear frequency was measured under the conditions of 79.4948544 MHz ( 29 Si nucleus), the spectrum width 40 kHz, and the pulse width 4.2 ⁇ sec (90 ° pulse).
  • the weight average molecular weight (Mw) in the following synthesis examples was measured by the following method.
  • the polystyrene conversion value was determined by GPC (gel permeation chromatography) using HLC-8220 (manufactured by Tosoh Corp.) as a measuring apparatus and using tetrahydrofuran as a developing solvent at a developing speed of 0.4 ml / min. .
  • Synthesis Example 1 Synthesis of cationically polymerizable group, radically polymerizable group, alkali-soluble group-containing polysiloxane (A-1) In a 500 ml three-necked flask, 22.21 g (0.090 mol) of ⁇ -glycidoxypropyltrimethoxysilane 67.40 g (0.300 mol) of p-styryltrimethoxysilane, 28.16 g (0.12 mol) of ⁇ -acryloylpropyltrimethoxysilane, 27.43 g (0.090 mol) of 3-triethoxysilylpropylsuccinic acid ), 0.287 g of TBC and 158.04 g of PGME, and while stirring at 40 ° C., an aqueous solution of dicyclohexylamine in which 0.726 g of dicyclohexylamine (0.50% by weight based on the charged monomer) is dissolved in
  • the flask was immersed in a 70 ° C. oil bath and stirred for 90 minutes. Thereafter, the oil bath was heated to 115 ° C. for 30 minutes. One hour after the start of heating, the internal temperature of the solution reached 100 ° C., and the mixture was heated and stirred for 2 hours (internal temperature is 100 to 110 ° C.) to obtain a solution of polysiloxane (A-1).
  • 0.05 L (liter) / minute flowed pressurized air during temperature rising and heating and stirring.
  • PGME was added so that the solid content concentration was 40% by weight.
  • the contents of the acryloyl group and the alkali-soluble group were 15 mol%, 50 mol%, 20 mol% and 15 mol%, respectively. Further, the weight average molecular weight of the obtained polysiloxane (A-1) was 2,500.
  • Synthesis Example 2 Synthesis of cationically polymerizable group, radically polymerizable group, alkali-soluble group-containing polysiloxane (A-2) In place of 22.21 g (0.090 mol) of ⁇ -glycidoxypropyltrimethoxysilane, 3- [( According to the same procedure as Synthesis Example 1 except that 25.10 g (0.090 mol) of 3-ethyloxetan-3-yl) methoxy] propyltrimethoxysilane was used, a polysiloxane (A-) having a solid content concentration of 40% by weight was used. The solution of 2) was obtained.
  • the contents of the acryloyl group and the alkali-soluble group were 15 mol%, 50 mol%, 20 mol% and 15 mol%, respectively.
  • the weight average molecular weight (Mw) of the obtained polysiloxane (A-2) was 2,400.
  • Styryl group (meth) acryloyl group, based on 100 mol% of the total content of (a1) cationically polymerizable group, (a2) radically polymerizable group and (a3) alkali-soluble group of the obtained polysiloxane (A-3)
  • the content of the alkali soluble group was 60 mol%, 20 mol%, and 15 mol%, respectively. Further, the weight average molecular weight (Mw) of the obtained polysiloxane (A-3) was 2,500.
  • Synthesis Example 4 Synthesis of cationically polymerizable group, radically polymerizable group, and alkali-soluble group-containing polysiloxane (A-4) 1.48 g (0.006 mol) of ⁇ -glycidoxypropyltrimethoxysilane in a 500 ml three-necked flask 86.27 g (0.384 mol) of p-styryltrimethoxysilane, 28.16 g (0.120 mol) of ⁇ -acryloylpropyltrimethoxysilane, 27.43 g (0.090 mol) of 3-triethoxysilylpropylsuccinic acid ), 0.343 g of TBC and 155.25 g of PGME are charged, and an aqueous solution of dicyclohexylamine in which 0.717 g of dicyclohexylamine (0.50% by weight to the charged monomer) is dissolved in 34.07 g of water while stirring at
  • Synthesis Example 5 Synthesis of cationically polymerizable group, radically polymerizable group, alkali-soluble group-containing polysiloxane (A-5) In a 500 ml three-necked flask, 44.42 g (0.18 mol) of ⁇ -glycidoxypropyltrimethoxysilane 47.18 g (0.21 mol) of p-styryltrimethoxysilane, 28.16 g (0.12 mol) of ⁇ -acryloylpropyltrimethoxysilane, 27.43 g (0.090 mol) of 3-triethoxysilylpropylsuccinic acid ), 0.226 g of TBC and 161.02 g of PGME, and while stirring at 40 ° C., an aqueous solution of dicyclohexylamine in which 0.736 g of dicyclohexylamine (0.50% by weight to the charged monomer) is dissolved in 34.07
  • Synthesis Example 6 Synthesis of cationically polymerizable group, radically polymerizable group, alkali-soluble group-containing polysiloxane (A-6)
  • A-6 alkali-soluble group-containing polysiloxane
  • An aqueous dicyclohexylamine solution in which 0.741 g of dicyclohexylamine (0.50% by weight based on the charged monomer) was dissolved in 34.07 g of water was added over 30 minutes while stirring at ° C.
  • Synthesis Example 7 Synthesis of cationically polymerizable group and alkali-soluble group-containing polysiloxane (A-7) In a 500 ml three-necked flask, 15.76 g (0.060 mol) of 3-trimethoxysilylpropylsuccinic acid and methyltrimethoxysilane 40.93 g (0.300 mol), 35.74 g (0.180 mol) of phenyltrimethoxysilane, 14.81 g (0.060 mol) of ⁇ -glycidoxypropyltrimethoxysilane, 100.28 g of PGME, 40 While stirring at .degree.
  • Synthesis Example 8 Synthesis of Radical Polymerizable Group-containing Polysiloxane (A-8) In a 500 ml three-necked flask, 33.65 g (0.150 mol) of p-styryltrimethoxysilane and 35.15 g of ⁇ -acryloylpropyltrimethoxysilane (0.150 mol), 0.206 g of TBC and 72.14 g of PGME are charged, while stirring at room temperature, 16.20 g of water and 0.34 g of dicyclohexylamine (0.50% by weight to the charged monomer) for 30 minutes Was added over.
  • Synthesis Example 9 Synthesis of cationically polymerizable group-containing polysiloxane (A-9) In a 500 ml three-necked flask, 34.05 g (0.250 mol) of methyltrimethoxysilane and 99.15 g (0.500 mol) of phenyltrimethoxysilane are contained.
  • the molar ratio of repeating units derived from methyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane and 3- (3,4-epoxycyclohexyl) propyltrimethoxysilane in the polysiloxane (A-9) is 25 each. It was mol%, 50 mol%, 15 mol%, 10 mol%. The weight average molecular weight of the obtained polysiloxane (A-9) was 4,200.
  • AD-2000 (trade name) manufactured by Takizawa Sangyo Co., Ltd.
  • shower development is performed for 60 seconds with a potassium hydroxide aqueous solution having a concentration of 0.045% by weight, and then rinsing for 30 seconds with water did.
  • Example 17 thereafter, using a parallel light mask aligner, using a super high pressure mercury lamp as a light source, a prebaked film through a pattern mask having a line and space pattern with a width of 10 to 200 ⁇ m or a gray scale mask for sensitivity measurement.
  • the exposure amount was changed from 50 mJ / cm 2 to 300 mJ / cm 2 by 50 mJ / cm 2 at a time.
  • an automatic developing apparatus (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.
  • shower development is performed for 90 seconds with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide, and then rinsed with water for 30 seconds.
  • an ultra-high pressure mercury lamp was used as a light source, and exposure was performed with an exposure amount of 500 mJ / cm 2 (i line) without using a photomask, and bleaching was performed.
  • the line and space pattern after development is magnified and observed at a magnification of 100 times using an optical microscope, and the exposure amount for forming a 50 ⁇ m line and space pattern in a width of 1: 1 is hereinafter referred to as the optimum exposure amount.
  • the sensitivity was taken as the sensitivity, and the minimum pattern size after development at the optimum exposure was taken as the resolution. Further, the development residue in the unexposed area was evaluated according to the following criteria. A: No development residue on unexposed area B: Development residue on unexposed area
  • Example 17 After that, shower development was performed for 90 seconds with a 2.38% by weight aqueous solution of tetramethylammonium hydroxide using an automatic developing apparatus (“AD-2000 (trade name)” manufactured by Takizawa Sangyo Co., Ltd.), Next, after rinsing for 30 seconds with water, using a parallel light mask aligner ("PLA-501F (trade name)” manufactured by Canon Inc.), using a super high pressure mercury lamp as a light source, the entire prebaked film is exposed at an exposure amount of 150 mJ / cm 2 It was exposed and cured in air at 100 ° C. for 30 minutes using an oven (“IHPS-222 (trade name)” manufactured by ESPEC Corp.) to prepare a cured film having a film thickness of 1.8 ⁇ m.
  • AD-2000 automatic developing apparatus
  • PPA-501F parallel light mask aligner
  • IHPS-222 (trade name)” manufactured by ESPEC Corp.
  • One hundred squares of 1 mm in size were prepared.
  • the adhesion was evaluated according to the following criteria based on the peeled area of the squares, and 4 or more was regarded as a pass.
  • Peeling area is 0% 4: Peeling area is 1% or more and less than 5% 3: Peeling area is 5% or more and less than 15% 2: Peeling area is 15% or more and less than 35% 1: Peeling area is 35% or more and less than 65% 0: Peeling area is 65 %that's all.
  • Viscosity change rate (%) (viscosity after storage (mPa ⁇ s)-viscosity before storage (mPa ⁇ s)) ⁇ 100 / (viscosity before storage (mPa ⁇ s))
  • Example 1 Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyl oxime) (B) as a photosensitizer under yellow light "IRGACURE” (registered trademark) OXE-02 (trade name) BASF Japan Ltd. (hereinafter referred to as "OXE 02") (0.080 g), bis (2,4,6-trimethyl benzoyl)-phenyl phosphine oxide ( 0.160 g of “IRGACURE” 819 (trade name) manufactured by BASF Japan Ltd.
  • IRGACURE registered trademark
  • OXE 02 bis (2,4,6-trimethyl benzoyl)-phenyl phosphine oxide
  • IC-819 dimethyl 2,2′-azobis (isobutyrate), 1,3-dioxohexahydrate Hydro-2H-4,7-methanoisoindol-2-yl trifluoromethanesulfonic acid
  • CGI-MDT trade name
  • ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] "" IRGANOX "(registered trademark) 245 (trade name)” BASF Japan 1.199 g of a 1% by weight solution of PGME (manufactured by KK) (C) 50 weight of PGMEA of 2-methacryloyloxyethyl acid phosphate ("Light Ester P-1M (trade name)” manufactured by Kyoeisha Chemical Co., Ltd.) (hereinafter "P-1M
  • Example 2 instead of the solution of the polysiloxane (A-1), 4.718 g of a solution of the polysiloxane (A-2), the epoxy compound 2,2 '-(((((1- (4-) instead of the cyclic ether compound OXT-191) (2- (4- (oxiran-2-ylmethoxy) phenyl) propan-2-yl) phenyl) ethane-1,1-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene))
  • Example 6 was carried out in the same manner as Example 1, except that 0.800 g of a 10% by weight solution of bis (oxirane) ("VG-3101L (trade name)" manufactured by Puretech Co., Ltd.) (hereinafter "VG-3101L”) was used.
  • the siloxane resin composition (P-2) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained siloxane resin composition (P-2).
  • Example 3 A siloxane resin composition (P-3) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-3) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-3).
  • Example 4 A siloxane resin composition (P-4) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-4) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-4).
  • Example 5 A siloxane resin composition (P-5) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-5) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-5).
  • Example 6 A siloxane resin composition (P-6) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-6) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-6).
  • Example 7 A siloxane resin composition (P-7) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-7) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-7).
  • Example 8 A siloxane resin composition (P-8) was obtained in the same manner as in Example 1 except that 4.718 g of a solution of polysiloxane (A-8) was used instead of the solution of polysiloxane (A-1). . Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-8).
  • Example 9 0.90 g of a 50 wt% PGMEA solution of 2-acryloyloxyethyl acid phosphate ("P-1A (trade name)" Kyoeisha Chemical Co., Ltd. product) instead of the polymerizable compound (P1-M) having a phosphorus atom
  • P-1A trade name
  • P1-M polymerizable compound having a phosphorus atom
  • Example 10 0.90 g (equivalent ratio) of a 50% by weight PGMEA solution of phosphoric acid-containing epoxy methacrylate “S-23A (trade name)” Dai-ichi Kogyo Seiyaku Co., Ltd. instead of the polymerizable compound (P1-M) having a phosphorus atom
  • a siloxane resin composition (P-11) was obtained in the same manner as in Example 1 except that .4) was used. Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-11).
  • a siloxane resin composition (P-12) was obtained in the same manner as in Example 1 except that .4) was used. Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-12).
  • Example 13 PGMEA 10 wt% of 3,3 ′-(oxybis (methylene)) bis (3-ethyl oxetane) (“OXT-221 (trade name)” manufactured by Toagosei Co., Ltd.) instead of the cyclic ether compound (OXT-191)
  • a siloxane resin composition (P-13) was obtained in the same manner as in Example 1 except that 0.800 g of the solution was used. Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-13).
  • Example 14 2,2 '-((((9H-fluorene-9,9-diyl) bis (4,1-phenylene)) bis (oxy)) bis (methylene) instead of cyclic ether compound (VG-3101 LOXT-191) ))
  • Example 6 was repeated except that 0.800 g of a 10 wt% PGMEA solution of bis (oxirane) ("PG-100 (trade name)" produced by Toagosei Co., Ltd.) was used, and a siloxane resin composition (P I got -14). Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-14).
  • Example 15 A siloxane resin composition (P-15) was obtained in the same manner as in Example 1 except that 4.918 g of a solution of polysiloxane (A-1) was used and no cyclic ether compound was added. Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-15).
  • Example 16 A siloxane resin composition (P-16) was obtained in the same manner as in Example 2 except that 4.918 g of a solution of polysiloxane (A-2) was used and no cyclic ether compound was added. Evaluation was performed in the same manner as Example 1 using the obtained siloxane resin composition (P-16).
  • F-554 trade name
  • Example 18 (C) 0.800 g of a 50 wt% solution of P-1M in PGMEA as a polymerizable compound having a phosphorus atom, and (D) a 50 wt% solution of PGMEA in a 3-ureidopropyltrimethoxysilane as a silane compound having a ureido group
  • Example 19 (C) 0.990 g of a 50 wt% solution of P-1M in PGMEA as a polymerizable compound having a phosphorus atom, and (D) a 50 wt% solution of PGMEA in a 3-ureidopropyltrimethoxysilane as a silane compound having a ureido group
  • compositions of Examples 1 to 19 and Comparative Examples 1 and 2 are shown in Tables 2 to 4, and the evaluation results are shown in Table 5.
  • the cured film obtained by curing the siloxane resin composition of the present invention includes various hard coat films such as protective films and insulating films of touch panels, insulating films for touch sensors, and flattening films for TFTs of liquid crystals and organic EL displays. It is suitably used for a metal wiring protective film, an insulating film, an antireflective film, an antireflective film, an optical filter, an overcoat for a color filter, a pillar material and the like.

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Abstract

L'invention concerne une composition de résine de siloxane qui a une excellente stabilité en stockage et qui peut être formée en un film durci ayant une excellente adhérence à un substrat en verre ou à un substrat métallique et une excellente résistance chimique, et ce même dans des conditions de durcissement à basse température de 100 °C ou moins. La composition de résine de siloxane contient (A) un polysiloxane, (B) un agent photosensible, (C) un composé polymérisable ayant un atome de phosphore et (D) un composé de silane ayant un groupe uréido.
PCT/JP2018/029343 2017-11-21 2018-08-06 Composition de résine de siloxane, film durci et dispositif d'affichage WO2019102655A1 (fr)

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CN201880075015.0A CN111373325B (zh) 2017-11-21 2018-08-06 硅氧烷树脂组合物、固化膜及显示装置
JP2018541436A JP7172598B2 (ja) 2017-11-21 2018-08-06 シロキサン樹脂組成物、硬化膜および表示装置
KR1020207004247A KR20200079231A (ko) 2017-11-21 2018-08-06 실록산 수지 조성물, 경화막 및 표시장치

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