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WO2011114995A1 - Agent de couplage de type silane, composition de résine photosensible de type négatif, pellicule durcissable et composant d'écran tactile - Google Patents

Agent de couplage de type silane, composition de résine photosensible de type négatif, pellicule durcissable et composant d'écran tactile Download PDF

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Publication number
WO2011114995A1
WO2011114995A1 PCT/JP2011/055680 JP2011055680W WO2011114995A1 WO 2011114995 A1 WO2011114995 A1 WO 2011114995A1 JP 2011055680 W JP2011055680 W JP 2011055680W WO 2011114995 A1 WO2011114995 A1 WO 2011114995A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
silane coupling
coupling agent
negative photosensitive
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2011/055680
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English (en)
Japanese (ja)
Inventor
岡沢徹
荒木斉
諏訪充史
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
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 Toray Industries Inc filed Critical Toray Industries Inc
Priority to SG2012068672A priority Critical patent/SG184100A1/en
Priority to CN201180014187.5A priority patent/CN102803274B/zh
Priority to KR1020127024097A priority patent/KR101839397B1/ko
Priority to JP2011526326A priority patent/JP5459315B2/ja
Publication of WO2011114995A1 publication Critical patent/WO2011114995A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • 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
    • G03F7/027—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
    • 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
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • H10P76/2041—
    • G02B1/105—
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings

Definitions

  • the present invention relates to a resin composition for forming a flattening film for a thin film transistor (TFT) substrate such as a liquid crystal display element or an organic EL display element, a protective film or insulating film such as a touch panel sensor element, or an interlayer insulating film of a semiconductor element.
  • TFT thin film transistor
  • the present invention relates to a silane coupling agent suitable for the above.
  • it is related with the negative photosensitive composition using the same, the cured film formed from it, and the member for touch panels which has the cured film.
  • hard coat materials there are various uses for hard coat materials. For example, it is used to improve the surface hardness of automobile parts, containers for cosmetics, sheets, films, optical disks, thin displays, and the like. Properties required for the hard coat material include heat resistance, weather resistance, adhesiveness, etc. in addition to hardness and scratch resistance.
  • a radical polymerization type UV curable hard coat material for example, see Non-Patent Document 1.
  • the composition of the hard coat material is a polymerizable group-containing oligomer, monomer, photopolymerization initiator, and other additives.
  • Oligomer and monomer are cross-linked by radical polymerization by UV irradiation to obtain a high hardness film. Since this hard coat material requires a short time for curing, use of this hard coat material improves productivity. Furthermore, since a negative photosensitive material having a general radical polymerization mechanism can be used, there is an advantage that the manufacturing cost is reduced.
  • the capacitive touch panel which has been attracting attention in recent years, is one of the uses of hard coat materials.
  • the capacitance type touch panel has a pattern made of an ITO (Indium Tin Oxide) film on glass.
  • ITO Indium Tin Oxide
  • a film having high hardness is required.
  • a method of adding a silane coupling agent is well known.
  • a silane coupling agent having an imide group see Patent Document 1 and Patent Document 2
  • Patent Document 3 a silane coupling agent suitable for the heat resistant resin precursor composition
  • a compound having a carboxyl group and an ester group or a carboxyl group and an amide group see Patent Document 3
  • organosilicon compound having an amic acid structure has a structure in which an amino group-containing silane coupling agent is added to an aromatic ring anhydride.
  • This organosilicon compound is strongly colored and is not suitable for touch panel applications, and the adhesion-improving curing is not sufficient.
  • An object of the present invention is to provide a cured film having excellent adhesion to a substrate surface composed of metal or inorganic material, high hardness, and excellent resolution. Furthermore, another object of the present invention is to provide a cured film having a low curing shrinkage rate and good flatness.
  • the present invention has the following configuration. That is, it is a silane coupling agent represented by the following general formula (1).
  • Each R 1 may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group may further have a substituent.
  • N represents 0 or 1.
  • R 2 represents carbon.
  • R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and phenoxy (In addition, among these groups of R 3 , those other than the hydroxyl group may further have a substituent.)
  • the cured film containing the silane coupling agent of the present invention has the effect of improving the adhesion with the substrate surface made of metal or inorganic material, having high hardness and excellent resolution. Furthermore, the cured film containing the silane coupling agent of the present invention has an effect that the curing shrinkage rate is low and the flatness is good.
  • the silane coupling agent of the present invention has a structure represented by the following general formula (1).
  • Each R 1 may be the same or different and represents an alkyl group having 1 to 6 carbon atoms.
  • the alkyl group may further have a substituent.
  • N represents 0 or 1.
  • R 2 represents carbon. Represents a trivalent organic group having 3 to 30.
  • R 3 may be the same or different and each represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a hydroxyl group, and phenoxy (In addition, among these groups of R 3 , those other than the hydroxyl group may further have a substituent.)
  • R 1 a methyl group, an ethyl group, and a butyl group are preferable, and a methyl group and an ethyl group are particularly preferable from the viewpoint of obtaining raw materials.
  • R 1 may have a substituent such as an alkoxy group, an aryl group, a phenoxy group, or a halogen group.
  • R 2 is preferably a trivalent organic group having 3 to 30 carbon atoms, and more preferably a trivalent organic group having 3 to 10 carbon atoms from the viewpoint of solubility in an organic solvent.
  • silane coupling agent represented by the general formula (1) of the present invention examples include 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butyl).
  • silane coupling agents When these silane coupling agents are added to the negative photosensitive resin, they may be used alone or mixed.
  • silane coupling agents As a method for producing these silane coupling agents, a method of producing by reacting a silane coupling agent containing an acid anhydride with an alkylamine is preferable from the viewpoint of ease of production.
  • a silane coupling agent containing an acid anhydride two types of silane coupling agents of the present invention are generated simultaneously.
  • a small amount of oligomer or the like can be replicated in this synthesis method, it does not significantly affect the adhesion improving effect and need not be considered.
  • the addition amount is preferably 1 to 15% by mass, preferably 3 to 10% by mass with respect to the total amount of the resin component of the negative photosensitive resin composition, that is, (B) alkali-soluble resin and (C) polyfunctional acrylic monomer. % Is more preferable. If the amount is less than 1% by mass, the effect of improving the adhesiveness is not sufficient.
  • the negative photosensitive resin composition using the silane coupling agent of the present invention comprises at least (A) a silane coupling agent represented by the general formula (1), (B) an alkali-soluble resin, and (C) a polyfunctional acrylic. It contains a monomer and (D) a photoradical polymerization initiator.
  • the negative photosensitive composition of the present invention contains (B) an alkali-soluble resin.
  • the alkali-soluble resin By having the alkali-soluble resin, the negative photosensitive resin composition is excellent in alkali solubility (developability), and a good pattern can be formed while suppressing the residue after development. Moreover, by having an ethylenically unsaturated double bond group, a crosslinking density can be improved and the hardness of a cured film can be improved.
  • alkali-soluble resin examples include polysiloxane, acrylic resin, vinyl ether resin, polyhydroxystyrene, novolac resin, polyimide, polyamide, and the like.
  • alkali-soluble resin it is preferable that at least a part of the ethylenically unsaturated double bond group is introduced in order to increase the hardness of the cured film.
  • polysiloxanes and acrylic resins are more preferred because of the ease of introduction of ethylenically unsaturated double bond groups. Moreover, you may contain 2 or more types of these polymers.
  • alkali-soluble resin it is not limited to this.
  • a reaction product obtained by hydrolyzing and condensing a trifunctional alkoxysilane compound is particularly preferable.
  • the following are mentioned as a trifunctional alkoxysilane compound.
  • the ethylenically unsaturated double bond group can be easily introduced into the polysiloxane, and the hardness of the cured film is increased. Is more preferable.
  • (Meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, cyclopropyl (meth) acrylate, cyclopentyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, cyclohexenyl (meth) acrylate, 4-methoxycyclohexyl (meth) acrylate, 2-cyclopropyloxycarbonylethyl (meth) acrylate, 2-cyclopentyloxycarbonylethyl (meth) acrylate, (meth) acrylic acid 2-cyclohexyloxycarbonylethyl, (meth) acrylic acid 2-cyclohexenyloxycarbonylethyl, (meth) acrylic acid 2- (4-methoxycyclohexyl)
  • Aromatic vinyl compounds such as styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, and ⁇ -methylstyrene may be copolymerized with the above (meth) acrylic acid or (meth) acrylic acid ester. .
  • an ethylenically unsaturated double bond group can be introduced by addition reaction of an epoxy compound having an ethylenically unsaturated double bond group with (meth) acrylic acid.
  • an epoxy compound having an ethylenically unsaturated double bond group include the following compounds.
  • the content of the (B) alkali-soluble resin is not particularly limited, and can be arbitrarily selected depending on the desired film thickness and application.
  • the alkali-soluble resin is preferably added in an amount of 10 to 60% by mass based on the solid content of the negative photosensitive resin composition.
  • the negative photosensitive composition of the present invention contains (C) a polyfunctional monomer.
  • the polyfunctional monomer refers to a compound having at least two ethylenically unsaturated double bonds in the molecule. Considering the ease of radical polymerization, a multi-sensitive monomer having an acrylic group is preferable.
  • Specific examples include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester, propylene phthalate anhydride Oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, oligomer such as alkyd modified (meth) acrylate, or tripropylene glycol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythrine Ritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dip
  • the negative photosensitive resin composition of the present invention contains (D) a photo radical polymerization initiator.
  • a photo radical polymerization initiator Any radical photopolymerization initiator may be used as long as it is decomposed and / or reacted by light (including ultraviolet rays and electron beams) to generate radicals.
  • light including ultraviolet rays and electron beams
  • ⁇ -aminoalkylphenone compounds 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, and the like.
  • acylphosphine oxide compound examples include 2,4,6-trimethylbenzoylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,6-dimethoxybenzoyl)-( 2,4,4-trimethylpentyl) -phosphine oxide and the like.
  • oxime ester compound 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, ethanone, 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) and the like.
  • 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, ethyl p-diethylaminobenzoate and the like.
  • the content of the radical photopolymerization initiator is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition. Moreover, 20 mass% or less is preferable and 10 mass% or less is more preferable. By setting it as the said range, radical hardening can fully be advanced and elution of the residual radical polymerization initiator etc. can be prevented and solvent resistance can be ensured.
  • the negative photosensitive resin composition of the present invention may contain a polymerization inhibitor.
  • a polymerization inhibitor By containing a polymerization inhibitor, the storage stability of the composition is improved, and the resolution after development is improved in applications requiring pattern processing.
  • Specific examples of the polymerization inhibitor include phenol, catechol, resorcinol, hydroquinone, 4-t-butylcatechol, 2,6-di (t-butyl) -p-cresol, phenothiazine, 4-methoxyphenol and the like.
  • the content of the polymerization inhibitor is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more in the solid content of the negative photosensitive resin composition.
  • it is preferably 5% by mass or less, and more preferably 1% by mass or less.
  • the negative photosensitive resin composition of the present invention may contain a thermal acid generator.
  • the effect of improving the adhesion of the silane coupling agent can be further enhanced by the thermal acid generator.
  • Specific examples of the thermal acid generator preferably used include triphenylsulfonium, 4-hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl- Examples include 4-acetylphenylmethylsulfonium, 2-methylbenzyl-4-benzoyloxyphenylmethylsulfonium, methanesulfonate, trifluoromethanesulfonate, camphorsulfonate, p-toluenesulfonate, and the like.
  • SI-60, SI-80, SI-100, SI-110, SI-145, SI-150, SI-200, SI-60L, SI-80L, SI-100L, SI-110L, SI-145L, SI -150L, SI-160L, SI-180L are also preferably used. Two or more of these may be contained.
  • the content of the thermal acid generator is preferably 0.1 to 3% by mass based on the total amount of the resin component of the negative photosensitive resin composition, that is, (B) alkali-soluble resin and (C) polyfunctional acrylic monomer. . If the amount is less than 0.1% by mass, the effect of improving the adhesiveness is small. If the amount is more than 3% by mass, the pattern becomes larger than the mask pattern and the resolution is lowered.
  • the siloxane resin composition of the present invention may contain an ultraviolet absorber.
  • an ultraviolet absorber By containing the 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.
  • a ultraviolet absorber There is no limitation in particular as a ultraviolet absorber, A well-known thing can be used.
  • benzotriazole compounds benzophenone compounds, and triazine compounds are preferably used.
  • ultraviolet absorbers for benzotriazole compounds include 2- (2H benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-t-pentylphenol, 2- (2H Benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-yl) -6-dodecyl-4-methylphenol, 2- (2 And '-hydroxy-5'-methacryloxyethylphenyl) -2H-benzotriazole.
  • UV absorbers for benzophenone compounds 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 negative 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 preferably used 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 contained. Further, a compound having a boiling point of 110 to 250 ° C. under atmospheric pressure is more preferable.
  • boiling point 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.
  • Specific examples of the compound having an alcoholic hydroxyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure include 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 Examples include ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, and 3-methyl-3-methoxy-1-butanol.
  • diacetone alcohol is preferable from the viewpoint of storage stability
  • propylene glycol mono t-butyl ether is preferable from the viewpoint of step coverage.
  • cyclic compound having a carbonyl group and having a boiling point of 110 to 250 ° C. under atmospheric pressure examples include ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, Examples include cycloheptanone. Among these, ⁇ -butyrolactone is preferable.
  • the negative photosensitive resin composition of the present invention may contain various solvents such as acetates, ketones and ethers other than those described above.
  • the content of the solvent is not particularly limited, and any amount can be used depending on the coating method.
  • the amount of solvent is generally 50 to 95% by mass of the entire negative photosensitive resin composition.
  • the negative 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. Specific examples include nitrogen-containing organic substances, silicone resin curing agents, various metal alcoholates, various metal chelate compounds, isocyanate compounds and polymers thereof, methylolated melamine derivatives, and methylolated urea derivatives. Two or more of these may be contained. Of these, metal chelate compounds, methylolated melamine derivatives, and methylolated urea derivatives are preferably used in view of the stability of the curing agent and the processability of the obtained coating film.
  • the negative photosensitive resin composition of the present invention may contain various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
  • various surfactants such as a fluorine-based surfactant and a silicone-based surfactant in order to improve the flowability during coating.
  • a fluorine-type surfactant, a silicone type surfactant, a polyalkylene oxide type surfactant, a poly (meth) acrylate type surfactant etc. can be used. Two or more of these may be used.
  • fluorosurfactants include “Megafac” (registered trademark) F142D, F172, F173, F183, F445, F470, F475, F477 (above, Dainippon Ink & Chemicals, Inc.) NBX-15 and FTX-218 (manufactured by Neos) are preferably used.
  • silicone surfactants BYK-333, BYK-301, BYK-331, BYK-345, BYK-307 (manufactured by BYK Japan Japan Co., Ltd.) are preferably used.
  • a typical method for producing the negative photosensitive resin composition of the present invention will be described.
  • a silane coupling agent represented by the general formula (1) (B) an alkali-soluble resin, (C) a polyfunctional acrylic monomer, (D) a photoradical polymerization initiator, and other additives as necessary. Is added to an arbitrary solvent and dissolved by stirring, and then the resulting solution is filtered to obtain a negative photosensitive resin composition.
  • the method for forming a cured film using the negative photosensitive resin composition of the present invention will be described with an example.
  • the negative photosensitive resin composition of the present invention is applied on a base substrate by a known method such as microgravure coating, spin coating, dip coating, curtain flow coating, roll coating, spray coating, slit coating, hot plate, Pre-bake with a heating device such as an oven. Pre-baking is performed in the range of 50 to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after pre-baking is preferably 0.1 to 15 ⁇ m.
  • exposure is performed using an exposure machine such as a stepper, a mirror projection mask aligner (MPA), or a parallel light mask aligner (PLA).
  • the exposure intensity is about 10 to 4000 J / m 2 (wavelength 365 nm exposure amount conversion), and this light is irradiated through or without a desired 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, and the like can be used.
  • the exposed portion can be dissolved by development to obtain a negative pattern.
  • 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. Specific examples include inorganic alkalis such as alkali metal hydroxides, carbonates, phosphates, silicates, borates, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, tetramethylammonium hydroxide. And aqueous solutions containing one or more quaternary ammonium salts such as choline. After development, it is preferable to rinse with water, followed by drying and baking in the range of 50 to 150 ° C.
  • this film is heated in a range of 150 to 450 ° C. for about 20 minutes to 1 hour with a heating device such as a hot plate or an oven.
  • the cured film obtained by curing the negative photosensitive resin composition of the present invention is used as a touch panel protective film, a touch panel insulating film, various hard coat materials, an antireflection film, and an optical filter. Further, since it has negative photosensitivity, it is suitably used for TFT flattening films, insulating films, antireflection films, color filter overcoats, column materials, etc. for liquid crystal and organic EL displays. Among these, in particular, it can be suitably used as a touch panel protective film or a touch panel insulating film that requires adhesion after heat treatment and chemical treatment to a substrate not containing Si, such as ITO or molybdenum.
  • Examples of the touch panel system include a resistance film type, an optical type, an electromagnetic induction type, and a capacitance type. Since especially high hardness is calculated
  • the hardness is preferably 4H or more
  • the transmittance is 95% or more
  • the resolution is preferably 20 ⁇ m or less.
  • the hardness and transmittance can be adjusted by selecting the exposure amount and the thermosetting temperature.
  • PGMEA propylene glycol monomethyl ether acetate
  • DAA diacetone alcohol
  • Synthesis Example 1 Synthesis of Silane Coupling Agent Mixed Solution (a-1) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine, and the mixture was allowed to warm to room temperature for a while. And stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 3- (tert-butylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid, 2- (2- (tert-butylamino) ) -2-Oxoethyl) -5- (trimethoxysilyl) pentanoic acid mixed solution (a-1) was obtained.
  • Synthesis Example 2 Synthesis of Silane Coupling Agent Mixed Solution (a-2) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of t-pentylamine were added for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (t-pentylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- ( A mixed solution (a-2) of tert-pentylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
  • Synthesis Example 3 Synthesis of Silane Coupling Agent Mixed Solution (a-3) To 200 g of PGMEA were added 41.97 g (160 mmol) of 3-trimethoxysilylpropylsuccinic anhydride and 9.45 g (160 mmol) of isopropylamine at room temperature for a while. After stirring, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2- (isopropylamino) -2-oxoethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (tert- A mixed solution (a-3) of isopropylcarbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
  • Synthesis Example 4 Synthesis of Silane Coupling Agent Mixed Solution (a-4) To 200 g of PGMEA was added 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 9.45 g (160 mmol) of n-propylamine for a while at room temperature. And then stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (propylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (propyl A mixed solution (a-4) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
  • Synthesis Example 5 Synthesis of Silane Coupling Agent Mixed Solution (a-5) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 14.90 g (160 mmol) of aniline were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 2- (2-oxo-2- (phenylamino) ethyl) -5- (trimethoxysilyl) pentanoic acid, 3- (phenyl A mixed solution (a-5) of carbamoyl) -6- (trimethoxysilyl) hexanoic acid was obtained.
  • Synthesis Example 6 Synthesis of Silane Coupling Agent Mixed Solution (a-6) To 200 g of PGMEA, 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 7.37 g (160 mmol) of ethanol were added and stirred at room temperature for a while. Then, the mixture was stirred at 40 ° C. for 2 hours. Then, it heated up to 80 degreeC and made it react for 6 hours.
  • the resulting solution was diluted with PGMEA so that the solid concentration was 20%, and 4-ethoxy-4-oxo-2- (trimethoxysilyl) butanoic acid, 4-ethoxy-4-oxo-3- (tri A mixed solution (a-6) of methoxysilyl) butanoic acid was obtained.
  • Synthesis Example 7 Synthesis of Silane Coupling Agent Solution (a-7) 41.97 g (160 mmol) of 3-trimethoxysilylpropyl succinic anhydride and 11.70 g (160 mmol) of t-butylamine were added to 400 g of PGMEA at room temperature for a while. After stirring, the mixture was stirred at 60 ° C. for 2 hours. Then, it heated up to 140 degreeC and made it react for 6 hours, azeotropically boiling PGMEA and water. The resulting solution was diluted with PGMEA so that the solid content concentration was 20% to obtain a 1- (tert-butyl) -3-trimethoxysilylpyrrolidine-2,5-dione solution (a-7).
  • Synthesis Example 8 Synthesis of Siloxane Resin Solution (b-1) 13.62 g (0.1 mol) of methyltrimethoxysilane, 118.98 g (0.6 mol) of phenyltrimethoxysilane, 3-trimethoxysilylpropyl succinic acid 39 .39 g (0.15 mol), ⁇ -methacryloxypropyltrimethoxysilane 35.16 g, and DAA 140.87 g were added to a 500 ml three-necked flask.
  • ITO substrate A cured film having a film thickness of 1.5 ⁇ m produced on this substrate (hereinafter referred to as ITO substrate) is made of ITO and a cured film according to JIS “K5400” 8.5.2 (1990) cross-cut tape method. Adhesion was evaluated. On the surface of the cured film on the glass substrate, 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm ⁇ 1 mm were produced. .
  • Example 1 Under a yellow light, 2-methyl- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name “Irgacure 907” manufactured by Ciba Specialty Chemicals Co., Ltd. (hereinafter referred to as IC907) .)) 1.557 g, 4,4-bis (diethylamino) benzophenone (hereinafter referred to as EK) 0.173 g was dissolved in 21.618 g DAA and 34.489 g PGMEA. To this solution, dipentaerythritol hexaacrylate (trade name “Kayarad DPHA”, Shin Nippon Kayaku Co., Ltd.
  • DPHA silane coupling agent mixed solution
  • a-1 silane coupling agent mixed solution
  • b-1 siloxane resin solution
  • BYK-333 which is a silicone surfactant (manufactured by BYK Japan Japan Co., Ltd.) 1.500 g of a 1% by weight PGMEA solution was added and stirred, followed by filtration with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-1).
  • the obtained negative photosensitive resin composition (N-1) was spin-coated on a glass substrate and an ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 ⁇ m.
  • the mask Using the parallel light mask aligner (PLA-501F manufactured by Canon Inc.) as the light source and the ultrahigh pressure mercury lamp as the light source, the mask having a one-to-one width of 5, 10, 20, 30, 40, 50 ⁇ m width
  • the exposure was performed at an exposure amount of 200 mJ (i-line) and a mask gap of 100 ⁇ m.
  • an automatic developing device AD-2000, manufactured by Takizawa Sangyo Co., Ltd.
  • shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (Mitsubishi Gas Chemical Co., Ltd.).
  • ELM-D Mitsubishi Gas Chemical Co., Ltd.
  • rinsed with water for 30 seconds.
  • a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). About the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the said method.
  • Example 2 A negative photosensitive resin composition (N-2) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-2).
  • Example 3 A negative photosensitive resin composition (N-3) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-3) was evaluated in the same manner as in Example 1.
  • Example 4 A negative photosensitive resin composition (Example 1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was changed to 0.433 g and the addition amount of PGMEA was changed to 38.382 g. N-4) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-4).
  • Example 5 The negative photosensitive resin composition (N-1) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 1.730 g and the addition amount of PGMEA was 37.085 g. -5) was obtained. Using the obtained negative photosensitive resin composition (N-5), evaluation was performed in the same manner as in Example 1.
  • Example 6 A negative photosensitive resin composition (N) was prepared in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 10.382 g and the addition amount of PGMEA was 28.433 g. -6) was obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-6).
  • Negative photosensitive resin composition (N-1) was carried out in the same manner as in Example 1 except that the addition amount of the silane coupling agent mixed solution (a-1) was 14.708 g and the addition amount of PGMEA was 24.107 g. -7) was obtained. Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-7).
  • Example 8 The negative photosensitive resin composition (N-1) (30.000 g) is triphenylsulfonium trifluoromethanesulfonate (trade name “WPAG-281”, manufactured by Big Chemie Japan Co., Ltd. (hereinafter referred to as WPAG-281). 0.052 g) was added and stirred to obtain a negative photosensitive resin composition (N-8), and the obtained negative photosensitive resin composition (N-8) was used as an example. Evaluation was performed in the same manner as in Example 1.
  • WPAG-281 triphenylsulfonium trifluoromethanesulfonate
  • Example 9 The negative photosensitive resin composition (N-9) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-1) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-9).
  • Example 10 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (21.629 g). In this solution, DPHA 8.652 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 21.629 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-10). Evaluation was carried out in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-10).
  • Example 11 A negative photosensitive resin composition (N-11) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-2) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-11).
  • Example 12 A negative photosensitive resin composition (N-12) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-3) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-12), evaluation was performed in the same manner as in Example 1.
  • Example 13 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (24.108 g).
  • DPHA 10.382 g silane coupling agent mixed solution (a-1) 4.326 g, 4-tert-butylcatechol PGMEA 1% by mass solution 8.652 g, acrylic resin solution (b-2) 17.303 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-13). Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-13).
  • Example 14 A negative photosensitive resin composition (N-14) was obtained in the same manner as in Example 13, except that 0.052 g of WPAG-281 was added to 30.000 g of the negative photosensitive resin composition (N-13). . Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-14).
  • Example 15 Under a yellow light, IC907 (1.557 g) and EK (0.173 g) were dissolved in DAA (32.000 g) and PGMEA (18.917 g). In this solution, DPHA 6.921 g, silane coupling agent mixed solution (a-1) 4.326 g, 4-t-butylcatechol PGMEA 1 mass% solution 8.652 g, acrylic resin solution (b-2) 25.955 g , 1.500 g of a 1 wt% PGMEA solution of BYK-333 was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a negative photosensitive resin composition (N-15). Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-15).
  • Example 16 Under a yellow light, 1.730 g of the quinonediazide compound (q-1) was dissolved in 6.045 g of DAA and 43.141 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Next, filtration was performed with a 0.45 ⁇ m filter to obtain a positive photosensitive resin composition (P-1).
  • a-1 silane coupling agent mixed solution
  • b-1 siloxane resin solution
  • BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Next,
  • the obtained positive photosensitive resin composition (P-1) was spin-coated on a glass substrate and an ITO substrate using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation number. Thereafter, these substrates were pre-baked for 2 minutes at 110 ° C. using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to produce a film having a thickness of 1.5 ⁇ m.
  • the mask Using the parallel light mask aligner (PLA-501F manufactured by Canon Inc.) as the light source and the ultrahigh pressure mercury lamp as the light source, the mask having a one-to-one width of 5, 10, 20, 30, 40, 50 ⁇ m width
  • the exposure was performed at an exposure amount of 200 mJ (i line) and a mask gap of 100 ⁇ m.
  • an unexposed portion having a sufficient area for hardness and adhesion measurement was secured.
  • an automatic developing device AD-2000, manufactured by Takizawa Sangyo Co., Ltd.
  • shower development was performed for 90 seconds with a 0.4% by mass tetramethylammonium hydroxide aqueous solution ELM-D (Mitsubishi Gas Chemical Co., Ltd.).
  • a cured film was prepared by curing in an air at 220 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). About the obtained cured film, hardness, adhesiveness, and resolution were evaluated by the said method.
  • Example 17 It was dissolved in 6.045 g of DAA and 44.871 g of PGMEA. In this solution, 4.326 g of the silane coupling agent mixed solution (a-1), 43.258 g of the siloxane resin solution (b-1), BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain a thermosetting resin composition (U-1).
  • a-1 silane coupling agent mixed solution
  • b-1 siloxane resin solution
  • BYK-333 which is a silicone-based surfactant (manufactured by Big Chemie Japan Co., Ltd.) 1.500 g of a 1% by weight solution of PGMEA was added and stirred. Subsequently, filtration was performed with a 0.45 ⁇ m filter to obtain
  • thermosetting resin composition (U-1) was spin-coated on a glass substrate and an ITO substrate, respectively, using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of revolutions. A 5 ⁇ m film was prepared. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222). Curing shrinkage was calculated by the above method, and hardness and adhesion were evaluated.
  • Comparative Example 2 A negative photosensitive resin composition (N-17) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. The obtained negative photosensitive resin composition (N-17) was used for evaluation in the same manner as in Example 1.
  • Comparative Example 3 A negative photosensitive resin composition (N-18) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-18).
  • Comparative Example 4 The negative photosensitive resin composition (N-19) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-17) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-19).
  • the negative photosensitive resin composition (N-20) was obtained by adding 0.208 g of WPAG-281 to 30.000 g of the negative photosensitive resin composition (N-16) and stirring. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-20).
  • Example 9 A negative photosensitive resin composition (N-24) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-4) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Using the obtained negative photosensitive resin composition (N-24), evaluation was performed in the same manner as in Example 1.
  • Comparative Example 10 A negative photosensitive resin composition (N-25) was prepared in the same manner as in Example 10 except that the silane coupling agent mixed solution (a-5) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-25).
  • Comparative Example 11 A negative photosensitive resin composition (N-26) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-6) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 using the obtained negative photosensitive resin composition (N-26).
  • Comparative Example 12 A negative photosensitive resin composition (N-27) was prepared in the same manner as in Example 1 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 1 by using the obtained negative photosensitive resin composition (N-27).
  • Comparative Example 13 A positive photosensitive resin composition (P-2) was prepared in the same manner as in Example 16 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). Obtained. Evaluation was performed in the same manner as in Example 16 using the obtained positive photosensitive resin composition (P-2).
  • thermosetting resin composition (U-2) was obtained in the same manner as in Example 17 except that the silane coupling agent mixed solution (a-7) was used instead of the silane coupling agent mixed solution (a-1). It was. Evaluation was performed in the same manner as in Example 17 using the obtained thermosetting resin composition (U-2).
  • Reference example 1 A negative photosensitive resin composition (N-1 (using a silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary rotation speed. Spin coated. Thereafter, prebaking was performed at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a film having a thickness of 1.5 ⁇ m. The produced film was exposed at an exposure amount of 200 mJ (i-line) using a parallel light mask aligner (PLA-501F manufactured by Canon Inc.) and an ultrahigh pressure mercury lamp as a light source.
  • N-1 using a silane coupling agent (a-1)
  • a spin coater (1H-360S manufactured by Mikasa Co., Ltd.)
  • prebaking was performed at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen M
  • Reference example 2 A positive photosensitive resin composition (P-1 (using silane coupling agent (a-1))) is applied to a silicon wafer substrate with a spin coater (1H-360S manufactured by Mikasa Co., Ltd.) at an arbitrary number of rotations. A film having a thickness of 1.5 ⁇ m was formed by spin coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.).
  • SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.
  • the curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the curing shrinkage ratio was 16%, and the planarization ability was poor. Evaluation was performed in the same manner as described above except that (P-2) was used instead of the positive photosensitive resin composition (P-1). As a result, the curing shrinkage ratio was 13% and the planarization ability was good.
  • the planarization performance tends to be lowered particularly by adding the silane coupling agent (a-1) of the present invention instead of the conventional silane coupling agent. It was seen.
  • thermosetting resin composition (U-1 (using silane coupling agent (a-1))) on a silicon wafer substrate at an arbitrary rotation speed using a spin coater (1H-360S manufactured by Mikasa Co., Ltd.).
  • a film having a thickness of 1.5 ⁇ m was prepared by coating. Thereafter, it was prebaked at 110 ° C. for 2 minutes using a hot plate (SCW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.). Finally, a cured film was produced by curing in an air at 260 ° C. for 1 hour using an oven (Espec Co., Ltd. IHPS-222).
  • the curing shrinkage rate was calculated by the above method, and the planarization ability was evaluated. As a result, the cure shrinkage ratio was 18%, and the planarization ability was poor.
  • thermosetting resin composition by adding the silane coupling agent (a-1) of the present invention instead of the conventional silane coupling agent, the curing shrinkage rate and the planarization performance are lowered. There was a trend.
  • the present invention is suitably used for a silane coupling agent, a negative photosensitive resin composition containing the same, a cured film using the same, and a touch panel device having the same.

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Abstract

La présente invention concerne un agent de couplage de type silane de formule générale (1). La présente invention concerne spécifiquement un agent de couplage de type silane améliorant de façon supérieure les propriétés adhésives vis-à-vis des surfaces de substrats constituées de métaux et de matériaux inorganiques, ainsi qu'une composition l'incluant. (Chacun des radicaux R1 peut être identique ou différent des autres et représente un groupement alkyle en C1-6.) Le groupement alkyle peut comporter des substituants supplémentaires. n représente 0 ou 1. R2 représente un groupement organique trivalent en C3-30. Chacun des radicaux R3 peut être identique ou différent des autres et représente un groupement alkyle en C1-6, un groupement alkoxy en C1-6, un groupement phényle, un groupement hydroxyle ou un groupement phénoxy. En outre, à l'exception du groupement hydroxy, ces groupements R3 peuvent être davantage substitués.
PCT/JP2011/055680 2010-03-17 2011-03-10 Agent de couplage de type silane, composition de résine photosensible de type négatif, pellicule durcissable et composant d'écran tactile Ceased WO2011114995A1 (fr)

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SG2012068672A SG184100A1 (en) 2010-03-17 2011-03-10 Silane coupling agent, negative-type photosensitive resin composition, curable film and touch panel component
CN201180014187.5A CN102803274B (zh) 2010-03-17 2011-03-10 硅烷偶联剂、负型感光性树脂组合物、固化膜、及触控面板用构件
KR1020127024097A KR101839397B1 (ko) 2010-03-17 2011-03-10 실란커플링제, 네거티브형 감광성 수지 조성물, 경화막, 및 터치 패널용 부재
JP2011526326A JP5459315B2 (ja) 2010-03-17 2011-03-10 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

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WO2013031753A1 (fr) * 2011-08-29 2013-03-07 東レ株式会社 Composition de résine colorée et substrat de matrice noire en résine
WO2013151167A1 (fr) * 2012-04-06 2013-10-10 Ａｚエレクトロニックマテリアルズマニュファクチャリング株式会社 Composition à base de siloxane photosensible négatif
JP2014005437A (ja) * 2011-11-21 2014-01-16 Toyo Ink Sc Holdings Co Ltd 樹脂組成物、ならびにそれを用いた保護膜およびタッチパネル用絶縁膜
JP2014066809A (ja) * 2012-09-25 2014-04-17 Asahi Kasei E-Materials Corp 感光性樹脂組成物
JP2014137394A (ja) * 2013-01-15 2014-07-28 Hitachi Chemical Co Ltd タッチパネル電極の保護膜用感光性透明材
WO2014126013A1 (fr) * 2013-02-14 2014-08-21 東レ株式会社 Composition de coloration photosensible de type négatif, film durci, motif écran à la lumière pour panneau tactile, et procédé de fabrication de panneau tactile
JP2015021029A (ja) * 2013-07-17 2015-02-02 東レ株式会社 組成物、これを用いた反射防止層およびその形成方法、ならびにそれを有するガラスおよび太陽電池モジュール
JP2015137271A (ja) * 2014-01-24 2015-07-30 信越化学工業株式会社 シランカップリング剤及びその製造方法、プライマー組成物並びに塗料組成物
WO2015194639A1 (fr) * 2014-06-20 2015-12-23 大阪有機化学工業株式会社 Composition photosensible et film durci constitué par cette composition
WO2018021049A1 (fr) * 2016-07-28 2018-02-01 日産化学工業株式会社 Composition de résine
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CN102803274B (zh) 2015-07-29
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