WO2014185435A1 - 絶縁材料用組成物 - Google Patents

絶縁材料用組成物 Download PDF

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WO2014185435A1
WO2014185435A1 PCT/JP2014/062767 JP2014062767W WO2014185435A1 WO 2014185435 A1 WO2014185435 A1 WO 2014185435A1 JP 2014062767 W JP2014062767 W JP 2014062767W WO 2014185435 A1 WO2014185435 A1 WO 2014185435A1
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composition
compound
acrylate
insulating material
ether
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PCT/JP2014/062767
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English (en)
French (fr)
Japanese (ja)
Inventor
正 中野
俊将 橋本
務 野々村
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ラサ工業株式会社
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Priority to JP2015517099A priority Critical patent/JP6055914B2/ja
Publication of WO2014185435A1 publication Critical patent/WO2014185435A1/ja

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    • 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
    • G03F7/027—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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—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
    • G03F7/085—Photosensitive compositions characterised by adhesion-promoting non-macromolecular additives
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer

Definitions

  • This invention relates to the composition for insulating materials used as the raw material of the insulating film formed in the surface of an electronic device.
  • a coating composition is formed by applying a raw material composition for an insulating film to a surface to be protected.
  • a step of placing a mask having a predetermined pattern on the coating film (3)
  • a step of curing a portion of the coating film not covered with the mask (4)
  • a developer The process of developing the mask pattern.
  • the developing step (4) is carried out, there has often been a problem that the developer enters between the cured film and the electronic device and the insulating coating is peeled off. Therefore, in forming the insulating coating on the electronic device, it is important to sufficiently adhere the insulating coating to the surface of the electronic device while ensuring the resistance of the insulating coating.
  • the physical properties such as resistance and adhesion of the insulating film are affected by the composition of the raw material composition constituting the insulating film.
  • a raw material composition of a conventional insulating film polysiloxane obtained by hydrolytic condensation of tetraethoxysilane and plural kinds of silane compounds, a compound having two or more ethylenically unsaturated groups, and a photo radical initiated polymerization agent Is known (for example, see Patent Document 1).
  • This raw material composition is applied onto a substrate, and the formed coating film is irradiated with radiation in a state where a photomask having a predetermined pattern is placed, and the unirradiated portion of the cured film is dissolved with an alkali developer. By removing, the insulating film of patent document 1 is formed.
  • an electronic device is composed of a plurality of different substances, and these are exposed on the surface.
  • the touch panel has a transparent electrode made of indium-tin oxide (ITO) and a drive circuit containing a metal such as molybdenum or aluminum on a glass substrate. Therefore, in order to improve the adhesion of the insulating film to the touch panel, it is necessary to use a material having high affinity for these different types of substances. Further, it is necessary to ensure the resistance (chemical resistance) of the insulating film to the developer so that the developer does not easily enter between the insulating film and the touch panel.
  • ITO indium-tin oxide
  • the raw material composition of Patent Document 1 used to form the insulating film is mainly composed of a silane compound
  • the insulating film formed from the raw material composition is not applied to the glass substrate. It is expected to show a certain degree of adhesion. However, it is difficult to increase the adhesion and resistance of the insulating coating even to ITO constituting the transparent electrode and the metal constituting the drive circuit.
  • the raw material composition of Patent Document 1 contains a compound having two or more ethylenically unsaturated groups in addition to the silane compound, which is added to improve the strength of the film, It does not function to improve adhesion and resistance.
  • the present invention has been made in view of the above problems, and is referred to as a raw material composition of an insulating film having excellent adhesion to an electronic device such as a touch panel (hereinafter referred to as “composition for insulating material”). ). Furthermore, it aims at providing the composition for insulating materials which has tolerance (chemical resistance) with respect to developing solutions, such as an organic solvent.
  • the characteristic configuration of the composition for insulating material according to the present invention is A siloxane oligomer having a crosslinkable functional group; A polymerization initiator; An adhesion promoter; It is to include.
  • the composition for an insulating material of this configuration includes a siloxane oligomer having a crosslinkable functional group, a polymerization initiator, and an adhesion promoter, an insulating film is formed on the surface of an electronic device using the composition for an insulating material.
  • good adhesion to the constituent materials (glass, ITO, and metal) of the electronic device can be realized.
  • the insulating coating can be prevented from peeling from the electronic device during pattern development with the developer and after pattern formation, and the quality of the electronic device can be stabilized.
  • the adhesion promoter preferably contains a coordination compound of aluminum and / or zirconium.
  • an aluminum and / or zirconium coordination compound as an adhesion promoter contained in an insulating material composition. It has been found that it exhibits excellent adhesion to all the constituent materials of the device (glass, ITO, and metal). Therefore, using the composition for an insulating material containing a siloxane oligomer having a crosslinkable functional group having this structure, a polymerization initiator, and an adhesion promoter containing a coordination compound of aluminum and / or zirconium, the surface of the electronic device is used. When the insulating film is formed, the adhesion effect of the insulating film to the electronic device can be improved. As a result, the insulating coating can be prevented from peeling from the electronic device during pattern development with the developer and after pattern formation, and the quality of the electronic device can be stabilized.
  • the adhesion promoter preferably contains a carbodiimide compound.
  • an insulating film is formed on the surface of an electronic device using a composition for an insulating material containing an adhesion promoter containing a siloxane oligomer having a crosslinkable functional group of this configuration, a polymerization initiator, and a carbodiimide compound, Good adhesion can be realized even for a drive circuit (including molybdenum) which has been difficult to adhere in the past.
  • the adhesion promoter preferably contains a mercaptosilane compound.
  • the mercaptosilane compound is conventionally used as an adhesive for a compound having a double bond such as rubber.
  • a mercaptosilane compound for a transparent electrode. It has been found that it has good adhesion to ITO. Therefore, when an insulating film is formed on the surface of an electronic device by using the composition for an insulating material containing a siloxane oligomer having a crosslinkable functional group of this configuration, a polymerization initiator, and an adhesion promoter containing a mercaptosilane compound, The adhesion effect of the insulating film to the electronic device can be further improved.
  • the siloxane oligomer having a crosslinkable functional group preferably contains trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate.
  • Trioxysilylalkyl acrylate and trioxysilylalkyl methacrylate are crosslinkable silane compounds containing an acrylic group having excellent transparency. Therefore, when the siloxane oligomer having a crosslinkable functional group is prepared so as to contain trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate, the transparency of the insulating coating can be improved.
  • composition for an insulating material according to the present invention It is preferable to further contain a polyfunctional acrylic monomer.
  • the polyfunctional acrylic monomer functions as a crosslinking agent for trioxysilylalkyl acrylate and trioxysilylalkyl methacrylate. Therefore, when the siloxane oligomer having a crosslinkable functional group contains trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate, when a polyfunctional acrylic monomer is used in combination, the composition for insulating material is crosslinked and cured. Since the sensitivity is improved and the crosslinking reaction can proceed even at a low temperature, a strong insulating film having good chemical resistance can be formed.
  • composition for an insulating material As the chemical resistance improver, a poly N-methoxymethyl compound or a photoacid generator is preferably contained.
  • the poly N-methoxymethyl compound is used as a thermal crosslinking agent, the photoacid generator is used as a resin curing agent, and these promote the polymerization of a siloxane oligomer having a crosslinkable functional group. Contribute to. Therefore, when a poly N-methoxymethyl compound or a photoacid generator is added as a chemical resistance improver to the composition for an insulating material, the polymerization of the siloxane oligomer having a crosslinkable functional group is promoted, and the formed insulating film Has a high hardness, and as a result, the chemical resistance of the insulating coating is improved.
  • FIG. 1 is a schematic view of a capacitive touch panel to which the composition for an insulating material of the present invention is applied.
  • a capacitive touch panel will be described as an example of an electronic device that is a target for forming an insulating film.
  • FIG. 1 is a schematic view of a capacitive touch panel 100 to which the composition for an insulating material of the present invention is applied.
  • the capacitive touch panel 100 includes a transparent electrode 20 made of ITO and a drive circuit 30 made of a metal material such as aluminum or molybdenum on a substrate glass 10.
  • a region where the substrate glass 10 is exposed is defined as a glass region A
  • a region where the transparent electrode 20 is present is defined as an ITO region B
  • a region where the drive circuit 30 is present is defined as a metal region C.
  • a composition for an insulating material is applied to the entire surface of the capacitive touch panel 100 and reacted to form an insulating film.
  • the composition for an insulating material of the present invention which is a raw material for the insulating film, includes (a) a siloxane oligomer having a crosslinkable functional group, (b) a polymerization initiator, and (c) an adhesion promoter as a basic composition. Including.
  • these basic compositions will be described.
  • Examples of n 4, 4-acryloxy-butyl trimethoxy silane, 4-acryloxy-butyl triethoxy
  • R ′ in the formula (1), when the carbon number of the alkyl group of R ′ exceeds 4, the hydrolysis polymerization reaction becomes extremely slow, so R ′ is a methyl group, an ethyl group, a propyl group, or a butyl group. It is preferable that a methyl group or an ethyl group is more preferable.
  • Examples of the phenyltrialkoxysilane used for hydrolysis copolycondensation include phenyltrimethoxysilane and phenyltriethoxysilane.
  • Examples of methyltrialkoxysilane used for hydrolysis copolycondensation include methyltrimethoxysilane and methyltriethoxysilane.
  • organosilane compounds include tetramethoxysilane, tetraethoxysilane, tetraacetoxysilane, tetraisocyanatosilane, tetrakis (acetoxime) silane, trimethoxysilane, triethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldiacetoxysilane, dimethylmethoxyacetoxysilane, Dimethyldiisocyanatosilane, dimethylmethoxyisocyanatosilane, dimethylbis (acetoxime) silane, methylvinyldimethoxysilane, methylphenyldime
  • Hydrolytic copolycondensation involves diluting the organic silane compound in a solvent such as ethanol, acetone, or butyl acetate as necessary, and then water and a catalytic amount of acid (hydrochloric acid, acetic acid, nitric acid, phosphoric acid, etc.) required for the reaction. ) Or a base (ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide, etc.) is added, and the reaction is performed under stirring and reflux conditions at an arbitrary temperature.
  • a solvent such as ethanol, acetone, or butyl acetate
  • acid hydrochloric acid, acetic acid, nitric acid, phosphoric acid, etc.
  • a base ammonia, triethylamine, cyclohexylamine, tetramethylammonium hydroxide, etc.
  • the siloxane oligomer having a crosslinkable functional group preferably contains trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate.
  • Trioxysilylalkyl acrylate and trioxysilylalkyl methacrylate are crosslinkable silane compounds containing an acrylic group having excellent transparency. For this reason, when the siloxane oligomer having a crosslinkable functional group is prepared so as to contain trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate, the transparency of the insulating coating can be improved.
  • the siloxane oligomer having a crosslinkable functional group contains trioxysilylalkyl acrylate or trioxysilylalkyl methacrylate
  • a polyfunctional acrylic monomer functions as a cross-linking agent for trioxysilylalkyl acrylate and trioxysilylalkyl methacrylate, which improves the sensitivity when the composition for insulating materials is cross-linked and cured, and further enables cross-linking reaction even at low temperatures. Can be advanced. As a result, a stronger insulating film can be formed.
  • polyfunctional acrylic monomer examples include (a-1) a bifunctional acrylate, (a-2) a trifunctional acrylate, and (a-3) a tetrafunctional or higher acrylate.
  • examples of usable polyfunctional acrylic monomers are as follows. In the following description, “(meth) acrylate” represents methacrylate or acrylate.
  • EO-modified refers to ethoxylated (meth) acrylate, specifically —OCOCH ⁇ CH 2 or —OCO—C (CH 3 ) ⁇ CH 2 instead of — (OC 2 H 4 ) n — OCOCH ⁇ CH 2 or — (OC 2 H 4 ) n —OCOC (CH 3 ) ⁇ CH 2 represents an ethoxy acrylate having a structure where n is a positive integer.
  • A-2) Trifunctional acrylate trimethylolpropane tri (meth) acrylate, EO modified trimethylolpropane tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, EO modified glycerin Tri (meth) acrylate, PO-modified glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, EO-modified pentaerythritol tri (meth) acrylate, PO-modified pentaerythritol tri (meth) acrylate, Tris (2-hydroxyethyl) Isocyanuric acid tri (meth) acrylate, ⁇ -caprolactone-modified tris (2-hydroxyethyl) isocyanuric acid tri (meth) acrylate, triallyl isocyanuric acid.
  • A-3) Tetrafunctional or higher acrylate ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, EO-modified ditrimethylol Propane tetra (meth) acrylate, EO modified pentaerythritol tetra (meth) acrylate, EO modified dipentaerythritol penta (meth) acrylate, EO modified dipentaerythritol hexa (meth) acrylate, PO modified ditrimethylolpropane tetra (meth) acrylate, PO-modified pentaerythritol tetra (meth) acrylate, PO-modified dipentaerythritol penta (me
  • (B) Polymerization initiator As the polymerization initiator, a photopolymerization initiator or a thermal polymerization initiator can be used, but a photoradical generator used in general negative photolithography is preferred. Specifically, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl-phenylketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one and 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl) Benzylmethyl ketals such as -propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one; 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl -2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one
  • the addition amount of the polymerization initiator is 0.5 to 40 parts by weight, preferably 1 to 20 parts by weight with respect to 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the addition amount is less than 0.5 parts by weight, the photosensitivity becomes insufficient.
  • (C) Adhesion promoter improves the adhesion of an insulating coating formed by reacting the composition for an insulating material of the present invention to an electronic device.
  • (c-1) a coordination compound of aluminum and / or zirconium
  • (c-2) a carbodiimide compound
  • (c-3) a mercaptosilane as particularly effective adhesion promoters.
  • the compound was found.
  • each compound will be described.
  • the coordination compound of aluminum and / or zirconium is preferably used in the form of a “chelate compound” which is a kind of “coordination compound”. Therefore, in the following description, the “coordinating compound of aluminum and / or zirconium” will be specifically described by taking “a chelate compound of aluminum and / or zirconium” as an example.
  • Aluminum and / or zirconium chelate compound is used as a substance for improving the adhesion of the insulating coating.
  • the chelate compound of aluminum and / or zirconium has adhesiveness regardless of the material. Therefore, the chelate compound of aluminum and / or zirconium is useful for improving the adhesion of the insulating coating to all of the glass region A, ITO region B, and metal region C shown in FIG.
  • An aluminum chelate compound can be synthesized by reacting an aluminum alkoxide with 0.5 to 3 equivalents of a chelating agent.
  • Aluminum alkoxides include trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tributoxyaluminum, triisobutoxyaluminum, trisec-butoxyaluminum, and tritert-butylaluminum.
  • a chelate compound of zirconium can be synthesized by reacting a zirconium alkoxide with 0.5 to 4 equivalents of a chelating agent.
  • Chelating agents used for the reaction with aluminum and zirconium include acetylacetone, cyclopentane-1,3-dione, cyclohexane-1,3-dione, benzoylacetone, methyl acetoacetate, ethyl acetoacetate, methyl benzoylacetate, benzoyl ⁇ -diketones such as ethyl acetate, methyl 4-methoxybenzoyl acetate, and ethyl 4-methoxybenzoyl acetate; triethanolamine, diethanolamine, N-methyldiethanolamine, monoethanolamine, N-methylethanolamine, and N, N— Examples include alkanolamines such as dimethylethanolamine.
  • the above aluminum chelate compound and zirconium chelate compound can be used as they are, but can also be used as a partial hydrolysis product to which a small amount of water is added.
  • the amount of the aluminum and / or zirconium chelate compound added is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the added amount is less than 0.1 parts by weight, the effect is not exhibited. If the added amount is more than 20 parts by weight, the hardness of the film is lowered, which may cause white turbidity and coloring.
  • (C-2) Carbodiimide compound The carbodiimide compound is originally used as a crosslinking agent, but in the present invention, it is used as a substance for improving the adhesion of the insulating coating.
  • the carbodiimide compound exhibits good adhesion particularly to a metal (such as molybdenum). Therefore, the carbodiimide compound is useful for improving the adhesion of the insulating film to the metal region C shown in FIG.
  • the carbodiimide compound has a —N ⁇ C ⁇ N— bond in the skeleton.
  • a carbodiimide compound is obtained by, for example, carbodiimidizing a polyisocyanate by a carbon dioxide condensation reaction in the presence of a phospholene-based carbodiimidization catalyst such as 3-methyl-1-phenyl-2-phospholene-1-oxide. can get.
  • polyisocyanate examples include hexamethylene diisocyanate, xylylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,12-diisocyanate decane, norbornane diisocyanate, 2,4-bis (8-isocyanate octyl) -1, Examples include 3-dioctylcyclobutane, 4,4′-dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, 2,4,6-triisopropylphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate, and tolylene diisocyanate. .
  • Commercially available carbodiimide resins such as carbodilite V-03, V-05, V-07, V-09 (manufactured by Nisshinbo Co., Ltd.) can also be used.
  • the addition amount of the carbodiimide compound is 0.5 to 200 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the added amount is less than 0.5 parts by weight, the effect is lost, and if it is more than 50 parts by weight, the heat resistance of the film is deteriorated, and it may cause cloudiness and coloring.
  • (C-3) Mercaptosilane Compound The mercaptosilane compound is originally used as an adhesive for a compound having a double bond such as rubber, but in the present invention, it is used as a substance for improving the adhesion of the insulating coating. used. Mercaptosilane compounds exhibit particularly good adhesion to ITO. Therefore, the mercaptosilane compound is useful for improving the adhesion of the insulating film to the ITO region B shown in FIG.
  • the mercaptosilane compound has the following general formula (2): (HS (CH 2 ) n ) 1-m (CH 3 ) m Si (OR) 3-m (2) n: an integer from 0 to 4 m: an integer from 0 to 1 R: a silane coupling agent having a mercapto group represented by any alkyl group.
  • silane coupling agent represented by formula (2) examples include trimethoxysilane thiol, triethoxysilane thiol, (mercaptomethyl) trimethoxysilane, (mercaptomethyl) triethoxysilane, and (2-mercaptoethyl) trimethoxy.
  • Silane (2-mercaptoethyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, (3-mercaptopropyl) triethoxysilane, (4-mercaptobutyl) trimethoxysilane, (3-mercaptobutyl) triethoxy Silane, methyldimethoxysilanethiol, methyldiethoxysilanethiol, methyl (mercaptomethyl) dimethoxysilane, methyl (mercaptomethyl) diethoxysilane, methyl (2-mercaptoethyl) dimethoxysilane, methyl (2- Lucatoethyl) diethoxysilane, methyl (3-mercaptopropyl) dimethoxysilane, methyl (3-mercaptopropyl) diethoxysilane, methyl (4-mercaptobutyl) dimethoxysilane, and methyl (3-mercaptobutyl) diethoxy
  • the addition amount of the mercaptosilane compound is 0.01 to 25 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the addition amount is less than 0.01 parts by weight, the effect is lost, and if it is more than 25 parts by weight, the heat resistance of the film is deteriorated. In addition, since it takes time to dry the membrane, it is also uneconomical.
  • composition for an insulating material of the present invention is an organic solvent used in the development step in addition to the above-mentioned (a) siloxane oligomer having a crosslinkable functional group, (b) a polymerization initiator, and (c) an adhesion promoter.
  • chemical resistance improvers can be included. Examples of the chemical resistance improver include (d-1) poly N-methoxymethyl compounds and (d-2) photoacid generators.
  • a poly N-methoxymethyl compound is used as a thermal crosslinking agent and contributes to the promotion of polymerization of a siloxane oligomer having a crosslinkable functional group in the present invention.
  • a poly N-methoxymethyl compound is a compound containing a methylated methylol group (NCH 2 OCH 3 ) bonded to one or more nitrogen atoms in the molecule.
  • a methylated methylol melamine resin such as Nicalac MW-30HM, MW-390, MW-100LM, MX-750LM (manufactured by Sanwa Chemical Co., Ltd.), Nicalac MX-270, MX-280, MX-290 Examples thereof include methylated urea derivatives represented by Sanwa Chemical Co., Ltd.
  • the composition for insulating material of the present invention contains a poly N-methoxymethyl compound, the formed insulating film has high hardness, and the resistance of the insulating film such as an organic solvent to the developer (chemical resistance) Will improve.
  • the amount of the poly N-methoxymethyl compound added is 0.01 to 25 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the addition amount is less than 0.01 parts by weight, the effect is lost, and if it is more than 25 parts by weight, the heat resistance of the film is deteriorated. In addition, since it takes time to dry the membrane, it is also uneconomical.
  • the photoacid generator is originally used as a curing agent such as an epoxy resin, and contributes to the promotion of polymerization of a siloxane oligomer having a crosslinkable functional group in the present invention.
  • a curing agent such as an epoxy resin
  • the photoacid generator one having sensitivity to g-line (wavelength 463 nm) or i-line (wavelength 365 nm) is used.
  • photocation generators such as onium salts that can be used for curing epoxy resins and having sensitivity on the lower wavelength side of less than 365 nm, and electron transfer dyes such as suitable acridine, coumarin, and aromatic condensed ring compounds It is also possible to use in combination with a sensitizer.
  • the photoacid generator can also be used in combination with the poly N-methoxymethyl compound described above.
  • the addition amount of the photoacid generator is 0.01 to 30 parts by weight, preferably 0.1 to 15 parts by weight, based on 100 parts by weight of the siloxane oligomer having a crosslinkable functional group. If the amount added is less than 0.01 parts by weight, the effect is lost. When the addition amount is more than 30 parts by weight, the photoacid generator remains as an unstable impurity in the film, and the characteristics (heat resistance, etc.) of the film are impaired. It is also uneconomical.
  • a composition for an insulating material is reacted by solution polymerization.
  • the composition for an insulating material is used in a state dissolved in (e) a solvent. Examples of usable solvents are shown below.
  • Ethers such as di-n-propyl ether, diisopropyl ether, di-n-butyl ether, di-n-amyl ether, methyltetrahydrofuran, and dioxane.
  • Glycol monoacylates such as ethylene glycol monoacetate, diethylene glycol monoacetate, triethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate.
  • Glycol diacylates such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, propylene glycol diacetate, propylene glycol diacetate, and propylene glycol diacetate.
  • Acetonitrile N-methylpyrrolidinone, N-ethylpyrrolidinone, N-propylpyrrolidinone, N-butylpyrrolidinone, N-hexylpyrrolidinone, N-cyclohexylpyrrolidinone, N, N-dimethylformamide, N, N-dimethylacetamide, and N, N-dimethyl sulfoxide and the like.
  • glycol ethers are preferable, and particularly preferable solvents are propylene glycol monomethyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether acetate.
  • said solvent can be used individually or in combination of 2 or more types.
  • composition for an insulating material of the present invention may contain (f) other additives.
  • Other additives are exemplified below.
  • additives oligomers such as polyurethane acrylate, polyepoxy acrylate, and acrylic-modified polydimethylsiloxane; surfactants; filler materials such as silica powder, alumina powder, and zirconia powder; pigments such as carbon black and phthalocyanine .
  • the addition amount of other additives is appropriately adjusted according to the type of additive, the formation conditions of the insulating film, and the like.
  • composition for an insulating material of the present invention was subjected to an evaluation test for adhesion to an electronic device and resistance to an organic solvent (chemical resistance).
  • the compositions for insulating materials prepared according to the present invention are designated as Examples 1 to 21, and the compositions for insulating materials prepared for comparison are designated as Comparative Examples 1 to 5.
  • ⁇ Adhesion test Examples 1 to 13 and Comparative Example 1> Assuming the glass region A, ITO region B, and metal region C in the capacitive touch panel 100 shown in FIG. 1, three types of substrates (glass substrate, ITO substrate, metal substrate) having different surface materials were produced.
  • As the glass substrate a chemically strengthened alkali aluminosilicate glass (Corning cover glass trade name “Gorilla (registered trademark)”, 0.7 mm thickness, 40.5 cm ⁇ 46 cm) ultrasonically cleaned with pure water was used.
  • As the ITO substrate after the glass substrate was washed, ITO was formed into a film with a thickness of 150 nm by a sputtering method, annealed in air at 150 ° C.
  • Table 1 shows the composition of the insulating material composition in Examples 1 to 13 and Comparative Example 1, and the results of the adhesion evaluation test of the insulating coating formed from the insulating material composition.
  • the composition for an insulating material was prepared as a coating solution by aging a mixture of the components according to the composition shown in Table 1 for a whole day and night.
  • the insulating composition (coating solution) was applied to each substrate using a spin coater (1000 rpm), dried at 100 ° C. for 1 minute, and then exposed to ultraviolet rays (wavelength: 365 nm, intensity: 100 mJ / cm 2 ).
  • the adhesion test is performed according to the cross-cut method, cross-cut tape method, and cross-cut method specified in the former “JIS K5400 Paint General Test Method”. Rated by stage. Specifically, eleven scratches were formed on the insulating coating on the substrate at intervals of 1 mm using a cutter knife, and a total of 100 square areas of 1 mm ⁇ 1 mm were formed. An adhesive tape was pressure-bonded onto this using a rubber roller, and then the adhesive tape was peeled off, and the number of square areas detached from the substrate was counted.
  • PMQC It is a phenylmethylsiloxane polymer containing 20 mol% of methacryloxy groups, and corresponds to the “siloxane oligomer having a crosslinkable functional group” described in the above embodiment.
  • PMQC is commercially available from APM and has, for example, the following chemical structural formula.
  • PGMEA Propylene glycol monomethyl ether acetate, which corresponds to the “solvent” described in the above embodiment.
  • BAPO Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, which corresponds to the “polymerization initiator” described in the above embodiment. BAPO is commercially available from BASF under the trade name “Irgacure (registered trademark) 819”.
  • MW-390 It is a methylated melamine resin and corresponds to the “poly N-methoxymethyl compound” described in the above embodiment. MW-390 is commercially available from Sanwa Chemical Co., Ltd.
  • AP-A This corresponds to the “aluminum chelate compound” described in the above embodiment.
  • AP-A was prepared by mixing 7.9 g of ethyl acetoacetate (manufactured by Wako Chemical Co.) with 10 g of aluminum tri-sec-butoxide (manufactured by Wako Chemical Co., Ltd.), left standing for 1 hour, and then adding 0.75 g of 1 mol / kg nitric acid aqueous solution. Added and diluted to 100 g with 2-propanol.
  • AP-Z This corresponds to the “zirconium chelate compound” described in the above embodiment.
  • AP-Z was prepared by mixing 8.2 g of ethyl acetoacetate (Wako Chemical Co., Ltd.) with 20 g of 80% zirconium tetra n-butoxide butanol solution (Aldrich Co., Ltd.), and allowing to stand for 1 hour. .75 g was added and diluted to 100 g with 2-propanol.
  • V-07 It is a modifier for carbodilite oil-based resin and corresponds to the “carbodiimide compound” described in the above embodiment. V-07 is commercially available from Nisshinbo Chemical Co., Ltd.
  • SHTES 3-Mercaptopropyltriethoxysilane, which corresponds to the “mercaptosilane compound” described in the above embodiment.
  • the insulating coating formed from the composition for insulating materials of Examples 1 to 13 prepared according to the composition of the present invention is 1B to 5B good for any of the glass substrate, ITO substrate, and metal substrate. Showed good adhesion. It was also confirmed that adhesion was improved when (c-1) an aluminum and / or zirconium chelate compound, (c-2) carbodiimide compound, and (c-3) mercaptosilane compound were used in combination as adhesion promoters. It was done. In particular, Example 13 using three types of adhesion promoters showed pore adhesion (5B) for all glass substrates, ITO substrates, and metal substrates. On the other hand, Comparative Example 1 containing no adhesion promoter resulted in poor adhesion (0B) to any of the glass substrate, ITO substrate, and metal substrate.
  • Table 2 summarizes the effects of using the adhesion promoter alone and in combination in the composition for insulating material.
  • ⁇ means poor adhesion
  • + means good adhesion
  • ++ means very good adhesion.
  • excellent adhesion could be obtained by combining an appropriate adhesion promoter depending on the type of substrate.
  • ⁇ Chemical resistance test Examples 14 to 21, Comparative Examples 2 to 5> A substrate on which an insulating film is formed is immersed in a drug (organic solvent) mixed with 60 parts by weight of dimethyl sulfoxide and 40 parts by weight of monoethanolamine in the same manner as in Examples 1 to 13 at 65 ° C. for 5 minutes.
  • the chemical resistance of the insulating coating was evaluated from the rate of change (%) in film thickness before and after.
  • the film thickness of the insulating coating was measured by a light interference type film thickness measuring device (NanoSpec / AFT 5100) manufactured by Nanometrics.
  • the film thickness of the insulating coating before immersion was 4.0 ⁇ m.
  • Table 3 shows the compositions of the compositions for insulating materials in Examples 14 to 21 and Comparative Examples 2 to 5, and the results of chemical resistance evaluation tests for insulating films formed from the compositions for insulating materials.
  • Table 3 For each composition shown in Table 3, the composition not shown in Table 1 is explained below.
  • the unit of the blending amount (numerical value) in each example and comparative example is parts by weight.
  • Table 3 also shows the results of the adhesion evaluation test.
  • TMPTA Trimethylolpropane acrylate, which corresponds to the “polyfunctional acrylic monomer” described in the above embodiment.
  • DPHA It is dipentaerythritol hexaacrylate and corresponds to the “multifunctional acrylic monomer” described in the above embodiment.
  • MMP Methyl methoxypropionate, which corresponds to the “solvent” described in the above embodiment.
  • TRI-A 2- (4-Methoxystyryl) -4,6-bistrichloromethyl-1,3,5-triazine, which functions as a photoacid generator.
  • ITX 2-Isopropylthioxanthone, which corresponds to the “polymerization initiator” described in the above embodiment.
  • DMAB-EH 4-Ethylhexyl 4-dimethylaminobenzoate functions as an auxiliary agent for the polymerization initiator.
  • Table 3 shows that the insulating film formed from the compositions for insulating materials of Examples 14 to 21 prepared according to the composition of the present invention has a small measured value of change in film thickness ( ⁇ 0.3% to 0.1%). ) Substantially no change in film thickness was observed. That is, it was confirmed that these insulating coatings have excellent resistance to solvents. On the other hand, in Comparative Examples 2 and 4 that did not contain a chemical resistance improver, the change in the film thickness of the insulating coating was large (15%, 18%), and it was not practically usable.
  • composition for an insulating material of the present invention can be used to form an insulating film used for an electronic device such as a touch panel and a flat panel display, but has excellent adhesion to metal and glass. It can also be used for surface treatment, decoration, painting, etc.

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JP2017120359A (ja) * 2015-12-24 2017-07-06 Jsr株式会社 半導体用ケイ素含有膜形成用材料及びパターン形成方法
JP2019144542A (ja) * 2018-02-22 2019-08-29 信越化学工業株式会社 レジスト材料及びこれを用いたパターン形成方法
WO2020095606A1 (ja) * 2018-11-07 2020-05-14 サカタインクス株式会社 皮膜形成用組成物、該皮膜形成用組成物を塗工してなるガラス基材、及び、該ガラス基材を用いてなるタッチパネル
KR20210135217A (ko) 2019-03-05 2021-11-12 도레이 카부시키가이샤 네가티브형 감광성 수지 조성물, 이것을 사용한 경화막의 제조 방법 및 터치패널
CN114573990A (zh) * 2022-03-11 2022-06-03 重庆大学 一种硬度、粘性可调节的聚硅氧烷及其制备方法

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JP2017120359A (ja) * 2015-12-24 2017-07-06 Jsr株式会社 半導体用ケイ素含有膜形成用材料及びパターン形成方法
JP2019144542A (ja) * 2018-02-22 2019-08-29 信越化学工業株式会社 レジスト材料及びこれを用いたパターン形成方法
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JP2020075992A (ja) * 2018-11-07 2020-05-21 サカタインクス株式会社 皮膜形成用組成物、該皮膜形成用組成物を塗工してなるガラス基材、及び、該ガラス基材を用いてなるタッチパネル
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KR20210135217A (ko) 2019-03-05 2021-11-12 도레이 카부시키가이샤 네가티브형 감광성 수지 조성물, 이것을 사용한 경화막의 제조 방법 및 터치패널
CN114573990A (zh) * 2022-03-11 2022-06-03 重庆大学 一种硬度、粘性可调节的聚硅氧烷及其制备方法
CN114573990B (zh) * 2022-03-11 2022-11-01 重庆大学 一种硬度、粘性可调节的聚硅氧烷及其制备方法

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