WO2020054335A1 - シリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物、及びシリコーン樹脂とポリオレフィン系樹脂との接着方法 - Google Patents
シリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物、及びシリコーン樹脂とポリオレフィン系樹脂との接着方法 Download PDFInfo
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- WO2020054335A1 WO2020054335A1 PCT/JP2019/032533 JP2019032533W WO2020054335A1 WO 2020054335 A1 WO2020054335 A1 WO 2020054335A1 JP 2019032533 W JP2019032533 W JP 2019032533W WO 2020054335 A1 WO2020054335 A1 WO 2020054335A1
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- 0 C*(C)CC(*)(*(C)C)C(OCCCN(C)O*(*)=C)=O Chemical compound C*(C)CC(*)(*(C)C)C(OCCCN(C)O*(*)=C)=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/002—Priming paints
-
- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/20—Diluents or solvents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J143/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
- C09J143/04—Homopolymers or copolymers of monomers containing silicon
Definitions
- the present invention relates to a primer composition for bonding a silicone resin and a polyolefin resin, particularly a cured product of a silicone rubber composition selected from a room temperature condensation-curable silicone rubber composition and an addition-curable silicone rubber composition (silicone rubber).
- the present invention relates to a primer composition used for bonding a silicone resin such as a cured product) to a polyolefin resin, and a method for bonding a silicone resin and a polyolefin resin using the primer composition.
- Polyolefin resins such as polypropylene and polyethylene are general-purpose thermoplastic resins, and are used in a wide range of fields because they are inexpensive and have many excellent properties such as mechanical properties, moldability, chemical resistance, and electrical properties. I have.
- polyolefin resins are known as poorly adhesive materials because they do not contain a polar group in the polymer and thus have low polarity and are crystalline.
- various methods are known, such as chemically treating the surface with a chemical or the like, or oxidizing the surface with a technique such as plasma treatment. These approaches require special equipment.
- a method of applying a chlorinated polyolefin or an acid-modified chlorinated polyolefin as a primer is known.
- a silicone sealant silicone resin
- a polyolefin resin a polyolefin resin
- Adhesion is obtained by treating the surface with a primer composed of polyolefin or acid-modified chlorinated polyolefin.
- Patent Document 1 JP-A-2004-210894
- the present invention has been made in view of the above circumstances, and is directed to a silicone resin, particularly a cured product of a silicone rubber composition selected from a room temperature condensation-curable silicone rubber composition and an addition-curable silicone rubber composition (a cured silicone rubber product). It is an object of the present invention to provide a primer composition which gives good adhesiveness in the adhesion between a silicone resin such as (1) and a polyolefin-based resin.
- the present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a (meth) acrylate monomer unit having a monovalent hydrocarbon group such as an alkyl group having 1 to 12 carbon atoms, A copolymer containing a (meth) acrylate monomer unit having a hydrosilyl group (SiH group) as a functional group capable of binding to a silicone resin such as a cured product (silicone rubber) of a curable or addition-curable silicone rubber composition
- a primer composition containing a coalesced product is a primer composition that gives good adhesiveness when a polyolefin-based resin is used as a base material, and completed the present invention.
- the present invention provides the following primer composition for bonding a silicone resin and a polyolefin resin, and a method for bonding a silicone resin and a polyolefin resin.
- R 1 is a hydrogen atom or a methyl group
- R 2 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
- ⁇ 2> The primer for bonding a silicone resin and a polyolefin-based resin according to ⁇ 1>, wherein R 2 in the (meth) acrylate monomer unit (A) in the component (I) is a tert-butyl group or a cyclohexyl group.
- Composition. ⁇ 3> The ratio of the (meth) acrylate monomer unit (A) :( meth) acrylate monomer unit (B) in the copolymer (I) is 1: 1 to 1000: 1 (molar ratio).
- ⁇ 4> The silicone resin and the polyolefin resin according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the component (I) is 0.1 to 20 parts by mass relative to 100 parts by mass of the component (II).
- the component (II) is one or a mixture of two or more selected from an aromatic hydrocarbon solvent, an alcohol solvent, a ketone solvent, an ether solvent, an ester solvent and a paraffin solvent.
- the copolymer (I) contains only (meth) acrylate monomer units (A) and (meth) acrylate monomer units (B) as monomer units ⁇ 1>
- ⁇ 9> After applying the primer composition for adhesion between the silicone resin and the polyolefin resin according to any one of ⁇ 1> to ⁇ 8> to the surface of a substrate made of a polyolefin resin to form the primer composition layer, On the outer surface of the primer composition layer, a silicone rubber composition selected from a room temperature condensation-curable silicone rubber composition and an addition-curable silicone rubber composition is further applied to form the silicone rubber composition layer.
- a method for bonding a silicone resin and a polyolefin resin comprising a step of curing a silicone rubber composition layer to form a silicone resin layer made of a cured silicone rubber.
- the primer composition of the present invention may be a silicone resin such as a cured product of a silicone resin composition selected from a room temperature condensation-curable silicone rubber composition and an addition-curable silicone rubber composition (silicone rubber cured product).
- a cured product (addition-curable silicone rubber cured product) such as an addition-curable silicone rubber composition that is crosslinked and cured by an addition reaction can be favorably adhered to a polyolefin-based resin, particularly polypropylene.
- the copolymer (I) used in the present invention comprises a (meth) acrylate monomer unit (A) represented by the following general formula (1), and a hydrosilyl group represented by the following general formula (2) ( That is, it contains at least a (meth) acrylate monomer unit (B) having a SiH group which is a hydrogen atom bonded to a silicon atom.
- R 1 is a hydrogen atom or a methyl group
- R 2 is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms.
- R 1 is a hydrogen atom or a methyl group
- R 3 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms
- R 4 is independently an unsubstituted or substituted A monovalent hydrocarbon group having 1 to 12 carbon atoms
- n is an integer satisfying 0 ⁇ n ⁇ 2.
- examples of the unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms for R 2 include a methyl group, an ethyl group, a propyl group, Alkyl groups such as isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cyclopentyl group, cyclohexyl group, etc.
- Alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, ⁇ -, ⁇ -naphthyl group; benzyl group, 2- An aralkyl group such as a phenylethyl group or a 3-phenylpropyl group; and a part or all of the hydrogen atoms of these groups are halogen atoms such as F, Cl, and Br.
- the (meth) acrylic acid ester monomer unit (A) is preferably a (meth) acrylic acid alkyl ester monomer unit or a (meth) acrylic acid cycloalkyl ester monomer unit.
- R 3 is a hydrogen atom or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, and is preferably unsubstituted or substituted. Is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
- alkyl group such as isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; Alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group and hexenyl group; aryl groups such as phenyl group, tolyl group, xylyl group, ⁇ -, ⁇ -naphthyl group; benzyl Aralkyl groups such as phenyl, 2-phenylethyl and 3-phenylpropyl groups; groups in which part or all of the hydrogen atoms of these groups have been substituted with halogen atoms such as F, Cl, Br, etc., cyano groups, etc.
- Examples thereof include a 3-chloropropyl group, a 3,3,3-trifluoropropyl group, a 2-cyanoethyl group and the like.
- an alkyl group such as a methyl group and an ethyl group is preferable, and a methyl group is particularly preferable.
- R 4 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group.
- cycloalkyl groups such as cyclopentyl groups and cyclohexyl groups
- An alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group
- an aryl group such as a phenyl group, a tolyl group, a xylyl group, an ⁇ -, ⁇ -naphthyl group
- a benzyl group a 2-phenylethyl group
- An aralkyl group such as a 3-phenylpropyl group; a part or all of the hydrogen atoms of these groups may be a halogen
- n is an integer satisfying 0 ⁇ n ⁇ 2 (that is, 0, 1 or 2), preferably 0 or 1, and more preferably 0.
- the molecular weight of the copolymer (I) is usually about 3,000 to 200,000, preferably about 5,000 to 100,000, and more preferably about 10,000 to 80,000.
- the molecular weight (or degree of polymerization) is usually measured as a polystyrene-equivalent number average molecular weight (or number average degree of polymerization) in gel permeation chromatography (GPC) analysis using tetrahydrofuran (THF) or the like as a developing solvent.
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the arrangement of the (meth) acrylate monomer unit (A) and the (meth) acrylate monomer unit (B) is not particularly limited. It may be in any form such as random, alternating, block or the like, but usually, a (meth) acrylate monomer unit (A) and a (meth) acrylate monomer unit ( And B) a random copolymer.
- the content of the component (I) in the primer composition of the present invention is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the component (II). It is preferably 1 to 10 parts by mass, more preferably 3 to 7.5 parts by mass.
- the copolymer (I) is a (meth) acrylate monomer (A) represented by the following general formula (3), which is a precursor of the (meth) acrylate monomer unit (A).
- the (meth) acrylate monomer (A) represented by the general formula (3) and the compound represented by the general formula (4) is added so as to have the above-mentioned molar ratio, and a polymerization initiator is further added thereto.
- the (meth) acrylic copolymer (I) is obtained in a form dissolved in the same solvent as in (1).
- the (meth) acrylate monomer represented by the general formula (3) include butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, and methacrylic acid.
- examples include cyclohexyl acrylate, butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, and cyclohexyl acrylate.
- One of these monomers may be used alone, or two or more thereof may be used.
- Examples of the (meth) acrylate monomer having a hydrosilyl group (SiH group) represented by the general formula (4) include [3- [tris (diorganohydrogensiloxy) silyl] propyl] acrylate and methacrylic acid.
- polymerization initiator to be used examples include organic peroxides such as di-tert-butyl peroxide, 2,2′-azobis (2-methylbutyronitrile), and 2,2′-azobis (isobutyroyl). It is preferable to use an azo compound such as nitrile).
- the amount of the polymerization initiator to be added is preferably 0.1 to 5.0 parts by mass based on 100 parts by mass of all the monomers.
- the copolymer (I) includes, in addition to the monomer represented by the general formula (3) and the monomer represented by the general formula (4), a (meth) acryl other than the above monomer.
- the acid ester may be added within a range that does not impair the object of the present invention.
- the copolymer (I) is a monomer unit of the (meth) acrylic acid ester monomer represented by the general formula (1). It is preferable that it contains only the body unit (A) and the (meth) acrylate monomer unit (B) represented by the general formula (2).
- Component (II) in the primer composition of the present invention may be any component that dissolves each component in the primer composition at an arbitrary ratio and has volatility at the same time.
- aromatic hydrocarbon solvents such as benzene, toluene, and xylene
- alcohol solvents such as methanol, ethanol, isopropyl alcohol, and ethylene glycol monomethyl ether
- Ketone solvents for example, ester solvents such as ligroin, ethyl acetate, butyl acetate, and isopropyl acetate
- ether solvents such as tetrahydrofuran and dioxane
- paraffin solvents such as hexane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
- aromatic hydrocarbon solvents or ester solvents are preferable, and ethylcyclohexane, ethyl acetate, isopropyl acetate and butyl acetate are particularly preferable.
- the primer composition of the present invention may include, besides the above-mentioned components, one of various alkoxysilanes and / or partially hydrolyzed condensates thereof, a silane coupling agent, a metal alkoxide, and the like as long as the object of the present invention is not impaired.
- two or more kinds can be blended as needed as optional components.
- alkoxysilane or the silane coupling agent examples include alkoxysilanes such as tetraethoxysilane, tetramethoxysilane, ethyl silicate, and methyl silicate or partial hydrolyzed condensates thereof, vinyltrimethoxysilane, vinyltriethoxysilane, ⁇ -methacrylic acid.
- the metal alkoxide examples include titanium alkoxides represented by titanium tetraalkoxides such as titanium tetraethoxide, titanium tetraisopropoxide and titanium tetrabutoxide; zirconium tetrapropoxide, zirconium tetra-n-butoxide, zirconium tetra-tert. Zirconium alkoxides represented by zirconium tetraalkoxides such as butoxide and the like.
- the compounding amount can be 0.1 to 20% by mass, particularly 0.1 to 10% by mass based on the whole primer composition.
- a platinum catalyst which is a catalyst for the addition reaction, is used to improve the stability of the composition. You may add in the amount which does not impair.
- a reinforcing filler a dye, a pigment, a heat resistance improver, and an antioxidant may be added as other optional components as long as the object of the present invention is not impaired.
- the primer composition of the present invention comprises a (meth) acrylate monomer having good wettability to a polyolefin resin and a (meth) acrylate ester having a hydroxysilyl group capable of forming a bond with an addition-curable silicone resin.
- Adhesion method between silicone resin and polyolefin resin As a method of bonding the silicone resin and the polyolefin-based resin according to the present invention, for example, after forming the primer composition layer by applying the primer composition of the present invention to the surface of a substrate made of a polyolefin-based resin, On the outer surface of the primer composition layer, a silicone rubber composition selected from a room temperature condensation-curable silicone rubber composition and an addition-curable silicone rubber composition is further applied to form the silicone rubber composition layer. A method of curing the silicone rubber composition layer to form a silicone resin layer made of a cured silicone rubber, thereby bonding the silicone resin and the polyolefin resin, and the like.
- the cured product of the addition-curable silicone rubber composition is obtained by curing at least an addition reaction-curable silicone composition containing a vinyl group-containing polyorganosiloxane, a polyorganohydrogensiloxane, and a platinum-based catalyst. It is preferably an elastic body.
- an addition reaction-curable silicone composition containing a vinyl group-containing polyorganosiloxane, a polyorganohydrogensiloxane, and a platinum-based catalyst. It is preferably an elastic body.
- other optional components such as a reaction control agent, a colorant, a flame retardant, a heat resistance improver, a plasticizer, reinforcing silica, and an adhesive may be added.
- the primer composition according to the present invention comprises a (meth) acrylate monomer (A) represented by the above general formula (3) and a hydrosilyl group represented by the above general formula (4).
- a suitable solvent preferably in the same solvent as the solvent (II)
- the polymerization initiator is added to the (meth) acrylic acid ester monomer (B) having the (SiH group) in the above-mentioned specific molar ratio. And then subjecting it to random copolymerization by means such as heating to prepare a (meth) acrylic copolymer (I), and then diluting the copolymer (I) to a specified concentration with the solvent (II).
- the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
- normal pressure means 1 atm and room temperature means 25 ⁇ 5 ° C.
- the molecular weight means a number average molecular weight in terms of polystyrene in GPC analysis using THF as a developing solvent for each (co) polymer prepared under the same conditions as in Examples and Comparative Examples.
- Example 1 At normal pressure, 300 g of ethyl acetate, 75.7 g (0.45 mol) of cyclohexyl methacrylate, and 19.0 g of [3- [tris (dimethylhydrogensiloxy) silyl] propyl] methacrylate in a 2,000 mL separable flask at normal pressure. (0.05 mol) and 0.6 g of 2,2′-azobis (2-methylbutyronitrile) (V-59 (manufactured by Wako Pure Chemical Industries, Ltd.)) were added, and the mixture was heated and stirred at 80 ° C. for 6 hours.
- V-59 2,2′-azobis (2-methylbutyronitrile
- Copolymer (I) 83 was prepared in the same manner as in Example 1 except that 64.0 g (0.45 mol) of tert-butyl methacrylate was used instead of 75.7 g (0.45 mol) of cyclohexyl methacrylate.
- the primers 1 to 5 prepared in the above Examples and Comparative Examples were thinly applied by brushing to the surfaces of two polypropylene resin adherends each having a width of 25 mm and a length of 100 mm.
- An addition-curable silicone rubber composition (KE-1825, manufactured by Shin-Etsu Chemical Co., Ltd.) is applied to a thickness of 1 mm between two adherends with the inner surfaces facing each other, and the coating is performed at 120 ° C. Heat-cured for 1 hour to form a cured silicone rubber layer (thickness: 1 mm) on two polypropylene resin adherends via a primer layer.
- Adhesive area 2.5 cm 2 (width 25 mm ⁇ length) 10 mm), and a shear adhesion test specimen having an adhesion thickness of 1 mm was prepared.
- the shear strength and cohesive failure rate of the test piece immediately after being prepared as described above were measured according to JIS K-6249 (shear adhesive test), and the cohesive failure rate of 80% or more (80 to 100%) was measured. If it was, it was recorded as ⁇ , if the cohesive failure rate was 50% or more and 79% or less, and ⁇ ⁇ ⁇ ⁇ if it was 49% or less.
- the present invention is not limited to the above embodiment.
- the above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect.
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Abstract
Description
<1>
下記一般式(1)
で表される(メタ)アクリル酸エステル単量体単位(A)、及び
下記一般式(2)
で表される(メタ)アクリル酸エステル単量体単位(B)を少なくとも含む共重合体(I)を、溶媒(II)中に含むことを特徴とするシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<2>
前記(I)成分における(メタ)アクリル酸エステル単量体単位(A)におけるR2が、tert-ブチル基又はシクロヘキシル基である<1>に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<3>
前記共重合体(I)における(メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)の割合が1:1~1000:1(モル比)である<1>又は<2>に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<4>
前記(I)成分の含有量が、(II)成分100質量部に対して0.1~20質量部である<1>~<3>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<5>
前記(II)成分が、芳香族炭化水素系溶媒、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、エステル系溶媒及びパラフィン系溶媒から選ばれる1種又は2種以上の混合物である<1>~<4>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<6>
前記プライマー組成物が室温縮合硬化型シリコーンゴム組成物又は付加硬化型シリコーンゴム組成物の硬化物をポリオレフィン系樹脂からなる基材に接着させるためのものである<1>~<5>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<7>
共重合体(I)の分子量が3,000~200,000である<1>~<6>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<8>
共重合体(I)が、単量体単位として(メタ)アクリル酸エステル単量体単位(A)及び(メタ)アクリル酸エステル単量体単位(B)のみを含有するものである<1>~<7>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
<9>
ポリオレフィン系樹脂からなる基材の表面に<1>~<8>のいずれかに記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物を適用して該プライマー組成物層を形成した後、該プライマー組成物層の外表面に、更に、室温縮合硬化型シリコーンゴム組成物及び付加硬化型シリコーンゴム組成物から選ばれるシリコーンゴム組成物を適用して該シリコーンゴム組成物層を形成し、該シリコーンゴム組成物層を硬化してシリコーンゴム硬化物からなるシリコーン樹脂層を形成する工程を有するシリコーン樹脂とポリオレフィン系樹脂との接着方法。
本発明のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物は、
成分(I):後述する所定の(メタ)アクリル共重合体、及び
成分(II):後述する所定の溶媒
を含むものである。
本発明で用いる共重合体(I)は、下記一般式(1)で表される(メタ)アクリル酸エステル単量体単位(A)、及び下記一般式(2)で表されるヒドロシリル基(即ち、ケイ素原子に結合した水素原子であるSiH基)を有する(メタ)アクリル酸エステル単量体単位(B)を少なくとも含むものである。
なお、nは0≦n≦2を満たす整数(即ち、0、1又は2)であり、好ましくは0又は1であり、より好ましくは0である。
このとき、(メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)の割合(以下、単に(A):(B)の割合と記す。)は1:1~1000:1(モル比)であることが好ましく、更に2:1~500:1、特に4:1~200:1、とりわけ6:1~100:1が好ましい。
なお、共重合体(I)中において、(メタ)アクリル酸エステル単量体単位(A)と(メタ)アクリル酸エステル単量体単位(B)の配列には特に制限はなく、この配列はランダム、交互、ブロック等のいずれの形態であってもよいが、通常は、ラジカル重合により生成する(メタ)アクリル酸エステル単量体単位(A)と(メタ)アクリル酸エステル単量体単位(B)とのランダム共重合体である。
本発明のプライマー組成物中の成分(II)は、プライマー組成物中の各成分を任意の割合で溶解し、同時に揮発性を有するものであればよい。具体的には、例えば、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒;例えば、メタノール、エタノール、イソプロピルアルコール、エチレングリコールモノメチルエーテル等のアルコール系溶媒;例えば、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン系溶媒;例えば、リグロイン、酢酸エチル、酢酸ブチル、酢酸イソプロピル等のエステル系溶媒;例えば、テトラヒドロフラン、ジオキサン等のエーテル系溶媒;例えば、ヘキサン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン等のパラフィン系溶媒が例示され、これらは1種単独でも2種以上の混合溶媒としても使用することができる。これらの中で、芳香族炭化水素系溶媒またはエステル系溶媒が好ましく、特にエチルシクロヘキサン、酢酸エチル、酢酸イソプロピル、酢酸ブチルが好ましい。
また本発明のプライマー組成物は、上述した成分以外にも、本発明の目的を損なわない範囲において、各種アルコキシシラン及び/又はその部分加水分解縮合物、シランカップリング剤、金属アルコキシド等の1種または2種以上を、任意成分として必要に応じて配合することができる。
本発明に係るシリコーン樹脂とポリオレフィン系樹脂とを接着する方法としては、例えば、ポリオレフィン系樹脂からなる基材の表面に本発明のプライマー組成物を適用して該プライマー組成物層を形成した後、該プライマー組成物層の外表面に、更に、室温縮合硬化型シリコーンゴム組成物及び付加硬化型シリコーンゴム組成物から選ばれるシリコーンゴム組成物を適用して該シリコーンゴム組成物層を形成し、該シリコーンゴム組成物層を硬化してシリコーンゴム硬化物からなるシリコーン樹脂層を形成することによってシリコーン樹脂とポリオレフィン系樹脂とを接着する方法などが挙げられる。
本発明にかかるプライマー組成物は、上記一般式(3)で表される(メタ)アクリル酸エステル単量体(A)と上記一般式(4)で表されるヒドロシリル基(SiH基)を有する(メタ)アクリル酸エステル単量体(B)とを適当な溶媒中(好ましくは上記溶媒(II)と同じ溶媒中)において、上記した特定のモル比で、重合開始剤を用いて加熱等の手段によってランダム共重合に付し(メタ)アクリル共重合体(I)を調製した後、上記溶媒(II)で規定の濃度に希釈することにより製造することができる。
常圧で、2,000mLセパラブルフラスコに、酢酸エチル300g、メタアクリル酸シクロヘキシル75.7g(0.45mоl)、メタアクリル酸[3-[トリス(ジメチルハイドロジェンシロキシ)シリル]プロピル]19.0g(0.05mоl)、及び2,2’-アゾビス(2-メチルブチロニトリル)(V-59(和光純薬工業(株)製))0.6gを仕込み、80℃で6時間加熱撹拌し、共重合体(I)94.7g((メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)=90:10(モル比)、単量体単位(A)と単量体単位(B)の配列はランダム、分子量:約50、000)を含む溶液を得た。該共重合体(I)を含む溶液に対して冷却後1200gの酢酸エチルで希釈して、プライマー1を得た。
メタアクリル酸[3-[トリス(ジメチルハイドロジェンシロキシ)シリル]プロピル]19.0g(0.05mоl)の代わりに、メタアクリル酸[3-[トリス(ジメチルハイドロジェンシロキシ)シリル]プロピル]1.9g(0.005mоl)を使用した以外は実施例1と同様にして、共重合体(I)77.6g((メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)=99:1(モル比)、単量体単位(A)と単量体単位(B)の配列はランダム、分子量:約40,000)を含む溶液を得た後、該共重合体(I)を含む溶液に対して冷却後1200gの酢酸エチルで希釈して、プライマー2を得た。
メタアクリル酸シクロヘキシル75.7g(0.45mоl)の代わりに、メタアクリル酸tert-ブチル64.0g(0.45mоl)を使用した以外は実施例1と同様にして、共重合体(I)83.0g((メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)=90:10(モル比)、単量体単位(A)と単量体単位(B)の配列はランダム、分子量:約50,000)を含む溶液を得た後、該共重合体(I)を含む溶液に対して冷却後1200gの酢酸エチルで希釈して、プライマー3を得た。
メタアクリル酸[3-[トリス(ジメチルハイドロジェンシロキシ)シリル]プロピル]を添加しなかった以外は実施例1と同様にして、メタアクリル酸シクロヘキシルの単独重合体75.7g(分子量:約40,000)を含む溶液を得た後、該単独重合体を含む溶液に対して冷却後1200gの酢酸エチルで希釈して、プライマー4を得た。
メタアクリル酸[3-[トリス(ジメチルハイドロジェンシロキシ)シリル]プロピル]の代わりに、メタアクリル酸[3-(トリメトキシシリル)プロピル]12.4g(0.05mоl)を使用した以外は実施例1と同様にして、ランダム共重合体88.1g(メタアクリル酸シクロヘキシル:メタアクリル酸[3-(トリメトキシシリル)プロピル]=90:10(モル比)、分子量:約50,000)を含む溶液を得た後、ランダム共重合体を含む溶液に対して冷却後1200gの酢酸エチルで希釈して、プライマー5を得た。
上記実施例及び比較例で調製されたプライマー1~5を、それぞれ幅25mm、長さ100mmのポリプロピレン樹脂製の被着体2枚の表面に、はけ塗りにより薄く塗布し、このプライマー塗膜面同士を内側に対向させた2枚の被着体の間に、付加硬化型シリコーンゴム組成物(KE-1825 信越化学工業(株)製)を厚さ1mmとなる様に塗布し、120℃で1時間加熱硬化して、2枚のポリプロピレン樹脂製被着体上にプライマー層を介してシリコーンゴム硬化物層(厚さ1mm)が形成された、接着面積2.5cm2(幅25mm×長さ10mm)、接着厚さ1mmの剪断接着試験体を作製した。
上記のようにして作製した直後の試験体について、JIS K-6249に準じて剪断接着力と凝集破壊率を測定し(せん断接着試験)、80%以上(80~100%)の凝集破壊率であれば〇、50%以上79%以下の凝集破壊率であれば△、49%以下の凝集破壊率であれば×と記録した。
Claims (9)
- 下記一般式(1)
で表される(メタ)アクリル酸エステル単量体単位(A)、及び
下記一般式(2)
で表される(メタ)アクリル酸エステル単量体単位(B)を少なくとも含む共重合体(I)を、溶媒(II)中に含むことを特徴とするシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。 - 前記(I)成分における(メタ)アクリル酸エステル単量体単位(A)におけるR2が、tert-ブチル基又はシクロヘキシル基である請求項1に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 前記共重合体(I)における(メタ)アクリル酸エステル単量体単位(A):(メタ)アクリル酸エステル単量体単位(B)の割合が1:1~1000:1(モル比)である請求項1又は2に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 前記(I)成分の含有量が、(II)成分100質量部に対して0.1~20質量部である請求項1~3のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 前記(II)成分が、芳香族炭化水素系溶媒、アルコール系溶媒、ケトン系溶媒、エーテル系溶媒、エステル系溶媒及びパラフィン系溶媒から選ばれる1種又は2種以上の混合物である請求項1~4のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 前記プライマー組成物が室温縮合硬化型シリコーンゴム組成物又は付加硬化型シリコーンゴム組成物の硬化物をポリオレフィン系樹脂からなる基材に接着させるためのものである請求項1~5のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 共重合体(I)の分子量が3,000~200,000である請求項1~6のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- 共重合体(I)が、単量体単位として(メタ)アクリル酸エステル単量体単位(A)及び(メタ)アクリル酸エステル単量体単位(B)のみを含有するものである請求項1~7のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物。
- ポリオレフィン系樹脂からなる基材の表面に請求項1~8のいずれか1項に記載のシリコーン樹脂とポリオレフィン系樹脂との接着用プライマー組成物を適用して該プライマー組成物層を形成した後、該プライマー組成物層の外表面に、更に、室温縮合硬化型シリコーンゴム組成物及び付加硬化型シリコーンゴム組成物から選ばれるシリコーンゴム組成物を適用して該シリコーンゴム組成物層を形成し、該シリコーンゴム組成物層を硬化してシリコーンゴム硬化物からなるシリコーン樹脂層を形成する工程を有するシリコーン樹脂とポリオレフィン系樹脂との接着方法。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004210894A (ja) | 2002-12-27 | 2004-07-29 | Yokohama Rubber Co Ltd:The | プライマー組成物 |
JP2010168496A (ja) * | 2009-01-23 | 2010-08-05 | Shin-Etsu Chemical Co Ltd | プライマー組成物およびそれを用いた光半導体装置 |
JP2014157849A (ja) * | 2013-01-18 | 2014-08-28 | Shin Etsu Chem Co Ltd | プライマー組成物及びそれを用いた光半導体装置 |
WO2017119181A1 (ja) * | 2016-01-08 | 2017-07-13 | 信越化学工業株式会社 | 積層体およびその製造方法 |
JP2019112580A (ja) * | 2017-12-26 | 2019-07-11 | 信越化学工業株式会社 | プライマー組成物及びシリコーン樹脂とポリオレフィン系樹脂との接着方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6040464B2 (ja) * | 1980-01-17 | 1985-09-11 | ホ−ヤ株式会社 | プライマ−の硬化方法 |
US20020015519A1 (en) * | 1998-12-11 | 2002-02-07 | Lord Corporation | Fiber substrate adhesion and coatings by contact metathesis polymerization |
JP2000281971A (ja) * | 1999-03-29 | 2000-10-10 | Shin Etsu Chem Co Ltd | シリコーン樹脂含有エマルジョン塗料組成物及びこの組成物の硬化被膜が形成された物品 |
CA2632633A1 (en) * | 1999-08-31 | 2001-02-28 | Weyerhaeuser Company | Coating for inhibiting stain formation in floor covering |
JP4573929B2 (ja) * | 1999-09-06 | 2010-11-04 | 中国塗料株式会社 | ポリシロキサン−アクリル樹脂ブロック共重合体組成物、防汚剤組成物、防汚塗膜、防汚処理基材、並びに基材の防汚処理方法 |
JP4394238B2 (ja) | 2000-02-28 | 2010-01-06 | 東レ・ダウコーニング株式会社 | 硬化性有機樹脂組成物および硬化樹脂 |
JP2003313332A (ja) | 2002-04-26 | 2003-11-06 | Kansai Paint Co Ltd | ポリオレフィン用プライマー |
JP2006063092A (ja) * | 2004-07-29 | 2006-03-09 | Dow Corning Toray Co Ltd | 硬化性オルガノポリシロキサン組成物、その硬化方法、光半導体装置および接着促進剤 |
DE102004044418A1 (de) * | 2004-09-14 | 2006-03-30 | Wacker Chemie Ag | Silicondecklack mit verbesserter Schmutzabweisung und verbesserter Verklebbarkeit mit Kernhülle-Partikel |
JP4771046B2 (ja) * | 2005-03-11 | 2011-09-14 | 信越化学工業株式会社 | 硬化性シリコーンゴム組成物及び液晶ポリマーとシリコーンゴムとの複合成形体の製造方法 |
JP5541939B2 (ja) * | 2010-02-01 | 2014-07-09 | 日東電工株式会社 | アクリル系粘着剤樹脂組成物およびそれを用いた粘着シート又は粘着テープ |
JP4749500B1 (ja) * | 2010-09-06 | 2011-08-17 | ハニー化成株式会社 | 水性表面処理剤組成物 |
JP5883030B2 (ja) * | 2010-12-29 | 2016-03-09 | スリーエム イノベイティブ プロパティズ カンパニー | シリコーン接着剤物品のための低粘着力バックサイズ及び方法 |
EP2808359B1 (en) * | 2012-03-02 | 2018-04-04 | Nippon Soda Co., Ltd. | Olefin based polymer-combined organic-inorganic composite and composition for forming same |
WO2015186515A1 (ja) * | 2014-06-06 | 2015-12-10 | 信越化学工業株式会社 | プライマー組成物 |
CN112011243B (zh) * | 2019-05-31 | 2022-11-11 | 信越化学工业株式会社 | 底涂剂组合物及使用了该底涂剂组合物的光学半导体装置 |
-
2019
- 2019-08-21 US US17/269,133 patent/US20210324224A1/en active Pending
- 2019-08-21 WO PCT/JP2019/032533 patent/WO2020054335A1/ja unknown
- 2019-08-21 KR KR1020217010285A patent/KR20210060505A/ko unknown
- 2019-08-21 JP JP2020546798A patent/JP7144762B2/ja active Active
- 2019-08-21 EP EP19861016.4A patent/EP3851502A4/en active Pending
- 2019-08-21 CN CN201980059032.XA patent/CN112673069A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2004210894A (ja) | 2002-12-27 | 2004-07-29 | Yokohama Rubber Co Ltd:The | プライマー組成物 |
JP2010168496A (ja) * | 2009-01-23 | 2010-08-05 | Shin-Etsu Chemical Co Ltd | プライマー組成物およびそれを用いた光半導体装置 |
JP2014157849A (ja) * | 2013-01-18 | 2014-08-28 | Shin Etsu Chem Co Ltd | プライマー組成物及びそれを用いた光半導体装置 |
WO2017119181A1 (ja) * | 2016-01-08 | 2017-07-13 | 信越化学工業株式会社 | 積層体およびその製造方法 |
JP2019112580A (ja) * | 2017-12-26 | 2019-07-11 | 信越化学工業株式会社 | プライマー組成物及びシリコーン樹脂とポリオレフィン系樹脂との接着方法 |
Non-Patent Citations (1)
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CN112673069A (zh) | 2021-04-16 |
EP3851502A4 (en) | 2022-06-08 |
KR20210060505A (ko) | 2021-05-26 |
EP3851502A1 (en) | 2021-07-21 |
US20210324224A1 (en) | 2021-10-21 |
JP7144762B2 (ja) | 2022-09-30 |
JPWO2020054335A1 (ja) | 2021-08-30 |
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