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WO2005087865A1 - Composition durcissable à l'humidité et procédé de collage - Google Patents

Composition durcissable à l'humidité et procédé de collage Download PDF

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Publication number
WO2005087865A1
WO2005087865A1 PCT/JP2004/003289 JP2004003289W WO2005087865A1 WO 2005087865 A1 WO2005087865 A1 WO 2005087865A1 JP 2004003289 W JP2004003289 W JP 2004003289W WO 2005087865 A1 WO2005087865 A1 WO 2005087865A1
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Prior art keywords
polymer
moisture
curable composition
hydrolysis
parts
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PCT/JP2004/003289
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English (en)
Japanese (ja)
Inventor
Shigeru Kurosawa
Yuichi Oshima
Masaaki Kishimoto
Yasunobu Horie
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Cemedine Co., Ltd.
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Publication date
Application filed by Cemedine Co., Ltd. filed Critical Cemedine Co., Ltd.
Priority to PCT/JP2004/003289 priority Critical patent/WO2005087865A1/fr
Publication of WO2005087865A1 publication Critical patent/WO2005087865A1/fr

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Classifications

    • 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
    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
    • C09J171/02—Polyalkylene oxides
    • 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
    • C09J133/00—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 at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/14—Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
    • C08L2666/22—Macromolecular compounds not provided for in C08L2666/16 - C08L2666/20
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/54—Inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a moisture-curable composition and a bonding method, and in particular, has excellent performance as an adhesive and a fixing agent for assembling electric products or precision equipment requiring flame retardancy, and has a long-term performance.
  • the present invention relates to a moisture-curable composition having excellent storage stability and a bonding method using the composition.
  • hagogen-based flame retardants represented by brominated flame retardants such as bromodiphenyl ether and tetrabromobisphenol A may cause metal corrosion and air pollution.
  • this halogen-based flame retardant greatly improves the flame retardant effect when used in combination with antimony oxide, there is also a problem that antimony oxide is undesirably toxic.
  • aluminum hydroxide / magnesium hydroxide which is a metal hydroxide, has recently been used as a halogen-free flame retardant for various plastics.
  • UL 94 evaluates the flame retardancy in electrical products and plastic materials, and UL 94 V-0 is specified as the class with the highest flame retardancy.
  • Japanese Patent Application Laid-Open No. 11-310682 describes a flame-retardant moisture-curable composition containing an acryl-based copolymer having a reactive silicon group and a metal hydroxide.
  • the moisture-curable composition has a problem in long-term storage stability because the liquid component of the composition bleeds out during long-term storage, and the one-component moisture-curable composition is used after stirring. It was extremely difficult to do so, so the period of use was limited. Disclosure of the invention
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, by combining a polymer having a reactive functional group, a metal oxide, and a surface-treated calcium carbonate, an adhesive, In addition to satisfying the basic performance as an agent, a flame-retardant cured product that passes UL 94 V-0 (sample thickness 1.5 mm) is obtained, and has long-term storage stability. They found that they were excellent and completed the present invention.
  • the present invention provides a moisture-curable composition having excellent performance as an adhesive and a fixing agent for assembling electric appliances or precision equipment requiring flame retardancy, and a bonding method using the same. The purpose is to:
  • (C) It is characterized by containing a surface-treated calcium carbonate having an average particle size of 0.01 to 10 m as an essential component.
  • acryl or methacryl is collectively described as (meth) acryl.
  • the polymer (A) has a force (A1) a reactive silicon group capable of being crosslinked by hydrolysis, and the molecular chain substantially has (1) an alkyl group having 1 to 8 carbon atoms. It is preferably a copolymer comprising an alkyl acrylate monomer unit and (2) a (meth) alkyl acrylate monomer unit having an alkyl group having 10 or more carbon atoms.
  • the metal hydroxide (B) power is preferably aluminum hydroxide and magnesium hydroxide.
  • the metal hydroxide (B) is preferably a metal hydroxide that has been treated with a force-printing agent, a fatty acid or a resin acid.
  • the use of the surface-treated metal hydroxide can improve the rate of increase in viscosity in storage stability and the electrical properties.
  • the surface-treated calcium carbonate (C) is preferably surface-treated calcium carbonate treated with a fatty acid or a resin acid.
  • the polymer (A) power The copolymer (A 1) and the polymer (A 1) It is preferable to use a mixture comprising a polymer (A 2) having a reactive silicon group capable of being bridged and having a molecular chain substantially consisting of an oxyalkylene monomer.
  • the mixing ratio of the two is not particularly limited, but it is preferable to mix 100 to 200 parts by weight of the polymer (A 2) with respect to 100 parts by weight of the copolymer (A 1). is there.
  • the finely divided silica is incorporated in an amount of 0.1 to 50 parts by weight based on 100 parts by weight of the polymer (A). It is preferable that the fine silica (D) is a hydrophobic silica treated with an aerosol silica or a force-printing agent [3].
  • the bonding method of the present invention is characterized in that parts of a flame-retardant product are bonded using the moisture-curable composition of the present invention.
  • Fig. 1 is a perspective view showing the structure of the deflection yoke and the locations where the adhesive is applied.
  • the moisture-curable composition of the present invention contains the following components (A), (B) and (C) as essential components.
  • the reactive group capable of being crosslinked by hydrolysis used in the present invention include, for example, a reactive silicon group and an isocyanate group. And a reactive silicon group is preferred.
  • the reactive silicon group has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and is a silicon-containing group that can be crosslinked by forming a siloxane bond, and is a silicon-containing group represented by the following formula (I). Groups are preferred.
  • R 1 may be the same or different and each is a substituted or unsubstituted monovalent organic group having 1 to 20 carbon atoms or a triorganosiloxy group, and X is a hydroxyl group or a heterogeneous or homologous group.
  • the polyurethane polymer having a reactive group capable of being crosslinked by hydrolysis is not particularly limited, but specific examples thereof include W98 / 58007, and JP-A-11-110. No. 0 4 27, JP 2000- 1 4 3 7 5 7 No. 3,300,020, JP-A-2000-169495, and other known urethane-based resins, and a urethane having an alkoxysilyl group. Based resins are preferred.
  • the (meth) acryl-based polymer having a reactive group capable of being crosslinked by hydrolysis is not particularly limited, and specific examples thereof include those described in JP-A-59-122254, Known reactivities described in JP-A-60-31556, JP-A-631-12642, JP-A-113-16282, etc.
  • (Meth) acrylic polymers having a reactive group are preferred, and (meth) acrylate copolymers having a reactive gayne group are preferred, having a reactive silicon group that can be crosslinked by hydrolysis,
  • the molecular chain is substantially composed of (1) an alkyl acrylate monomer unit having an alkyl group having 1 to 8 carbon atoms (meth) and (2) an alkyl group having 10 or more carbon atoms (meth) It is particularly preferable to use a copolymer (A 1) comprising an acrylic acid alkyl ester monomer unit.
  • the silicone having a reactive group that can be crosslinked by hydrolysis is not particularly limited, but specific examples thereof are described in Japanese Patent Application Laid-Open No. H10-316568, Japanese Patent Laid-open No. Hei 11-20996.
  • Known room-temperature-curable organopolysiloxanes described in JP-A No. 20 and JP-A No. 2001-200161 are listed.
  • the above-mentioned polyoxyalkylene polymer having a reactive group capable of being crosslinked by hydrolysis is not particularly limited, but specific examples thereof are described in JP-B-45-36319, JP-B No. 46-121254, Japanese Patent Publication No. 49-32673, and Japanese Patent Application Laid-Open No. 50-15659, each of which has a reactive silicon group.
  • a xyalkylene-based polymer is exemplified.
  • the (meth) acrylic polymer having the reactive group, the polyoxyalkylene polymer having the reactive group, and a mixture thereof are more likely to cause a contact failure than the silicone having the reactive group. It is suitable because it does not contain or generate low molecular cyclic siloxanes, which are factors.
  • the (meth) acrylic ester copolymer having a reactive silicon group has a high viscosity at a polymerization degree of about 300 to 600, so that a plasticizer, a polyether polyol and a solvent are used. Workability may be poor unless diluted with liquids such as.
  • a polyoxyalkylene-based polymer having a reactive silicon group has the same degree of polymerization and a lower viscosity than a (meth) acrylate-based copolymer. Therefore, in order to improve workability such as coatability, the (meth) acrylic acid ester-based copolymer having a reactive silicon group and the oxyalkylene-based polymer having a reactive silicon group are used in combination.
  • a non-solvent type flame retardant composition can be constituted.
  • the mixing ratio is not particularly limited, but the ratio of the reactive silicon group-containing polyoxyalkylene polymer to the reactive silicon group-containing (meth) acrylic acid ester copolymer is 100 parts by weight. It is preferable to add 0 to 200 parts by weight.
  • a curing catalyst is used in the curable composition of the present invention. The curing catalyst is not particularly limited as long as it is a catalyst that crosslinks the polymer (A).
  • dibutyltin dilaurate dibutyltin oxide, dibutyltin diacetate, dibutyltin distearate, dibutyltin laurate oxide, dibutyltin diacetylacetonate, dibutyltin Tin compounds such as tin dioleyl malate, dibutyl tin octate, dioctyl tin oxide, dioctyl tin dilaurate; metal complexes such as tetra-n-butoxy titanate and tetraisopropoxy titanate Titanate-based compounds; Lead octylate, lead naphthenate, nickel naphthenate, cobalt naphthenate, zinc-based compounds, iron-based compounds, bismuth, etc.
  • Metal sulphonate; aluminum acetylacetonate complex, vanadium acetyla Metal acetyl acetonate complexes such as setnato complex are exemplified.
  • amine salts such as dibutylamine-2-ethylhexoate, organic phosphoric compounds such as monomethylphosphoric acid and di-n-butylphosphoric acid, and other acidic and basic catalysts can be used. These may be used alone or in combination of two or more.
  • metal hydroxide (B) aluminum hydroxide and magnesium hydroxide are preferably used.
  • the metal hydroxide may be used without surface treatment, or may be used after surface treatment with a treating agent such as a coupling agent, a fatty acid or a resin acid. These may be used alone or in combination of two or more.
  • Examples of the coupling agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes.
  • Specific organic titanate compounds include, for example, tetrapropoxytitanium, tetrabutoxytitanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxytitanium, diproxyl bis (acetylacetonato) titanium, titanium propoxyoctylene Glycolate, Titanium stearate, Isopirvir triisostearate ltitanate, Isopropyl tridodecylbenzenesulfonyl nitrate, Isoprovir tris (dioctyl pyrophosphate) titanate, Tetraisopropyl bis (Dioctyl phosphite) ) Titanate, Tetraoctyl bis (ditridecyl phosphite
  • Organic aluminum compounds such as acetoalkoxy aluminum dimethyl diisopropylate and organic zirconium compounds such as zirconium butylate, zirconium acetyl acetate, acetyl acetonyl dimethyl butyrate, zirconium lactate, and zirconium butyl stearate can be used.
  • silane compound examples include vinyl trimethoxy silane, vinyl triethoxy silane, pis tris (2-methoxetoxy) silane, N— (2-aminoethyl) 3-aminopropyl methyl dimethoxy silane, and N- (2-amino) Ethyl) 3-aminopropylmethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylpyrutriethoxysilane, 3-glycidoxypropylpyrutrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4 1-epoxycyclohexyl) ethyltrimethoxysilane, 3-clopropylpropyltrimethoxysilane, 3-clopropylpropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxy Silane
  • fatty acids examples include saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and araginic acid, oleic acid, elaidic acid, linoleic acid, Examples include unsaturated fatty acids such as cinnolic acid, and alicyclic carboxylic acids such as naphthenic acid.
  • Examples of the resin acid include abichenic acid, pimaric acid, pallastrinic acid, neoabietic acid and the like.
  • Aluminum hydroxide, magnesium hydroxide, or a mixture thereof releases structural water at approximately 180 to 320 ° C, which is consistent with the decomposition temperature of the polymer material, so that flame ignition and fire spread can be prevented. Can exhibit excellent flame retardancy.
  • metal hydroxide is a coupling agent treated with an aromatic amine, phenol, naphthols or an active methylene compound, or a surface treated with a fatty acid or a resin acid, a slight amount of Flame retardant effect is reduced, but viscosity stability and electrical properties are improved.
  • the particle size of the metal hydroxide is 0.1 / Im to 200 m, preferably 0.3 m to 100 m, more preferably 0.3 m to 30 m. preferable.
  • the amount of the metal hydroxide is preferably 50 parts by weight to 350 parts by weight based on 100 parts by weight of the polymer (A), and is preferably 80 parts by weight to 280 parts by weight. Is more preferable, and 110 parts by weight to 230 parts by weight is most preferable. If the amount of the metal hydroxide is less than 50 parts by weight, sufficient flame retardancy cannot be obtained. For example, when ignited, fire may continue to spread or the polymer may depolymerize and liquefy. If the amount is more than 50 parts by weight, the viscosity of the composition increases and the workability deteriorates, and the basic physical properties such as adhesive strength cannot be maintained. The flame retardant effect also differs slightly depending on the particle size of the metal hydroxide.
  • the above-mentioned flame retardants such as halogen-based, phosphorus-based, and antimony oxide have the above-mentioned problems in ordinary use, but in the present invention, these flame retardants can be used in combination with metal hydroxides. It is. In addition, zinc borate, zinc stannate and the like can also be added since they have a smoke reducing effect.
  • As the surface-treated calcium carbonate (C) a known surface-treated carbonated calcium carbonate having an average particle size of 0.01 to 10 m can be widely used.
  • the surface treating calcium carbonate treating agent include saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and araginic acid, and oleic acid.
  • saturated fatty acids such as caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, and araginic acid, and oleic acid.
  • Unsaturated fatty acids such as elaidic acid, linoleic acid, and ricinoleic acid; alicyclic carboxylic acids such as naphthenic acid; resin acids such as avicenic acid, pimaric acid, norlastric acid, and neoabietic acid And the like.
  • Calcium carbonate treated with sulfonic acids, alkali metal salts, alkaline earth metal salts, ammonium salts, and amine salts can also be used.Furthermore, anionic, ionic, and nonionic surfactants can be used. Also use the treated calcium carbonate.
  • the amount of the surface-treated calcium carbonate is preferably 1 to 200 parts by weight, more preferably 3 to 70 parts by weight, based on 100 parts by weight of the polymer (A). , 5 to 40 parts by weight are most preferred. If the amount of the surface-treated calcium carbonate is more than 200 parts by weight, sufficient flame retardancy can be obtained, but the viscosity of the composition becomes high, causing a problem in workability.
  • Untreated calcium carbonate, talc, clay, magnesium carbonate, anhydrous silicon, hydrated silicon, calcium silicate, shirasu balloon, glass balloon, and the like may be further added. May improve.
  • the component (D) finely divided silica As the finely divided silica, aerosol silica or hydrophobic silica treated with a force-removing agent is preferred. Used.
  • the amount of the fine silica is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the polymer (A).
  • ultraviolet absorbers can also be added as other additives.
  • antioxidants can also be added as other additives.
  • silane coupling agents aminosilane, epoxysilane, acrylic silane, vinylsilane, mercaptosilane, isocyanate silane, etc.
  • the residual carbon ratio is improved and the drip property (dropping during combustion) is improved, so that the amount of the metal hydroxide is reduced. it can.
  • Silicone compounds commercially available as flame retardants can be used as non-halogen flame retardant aids.
  • the bonding method of the present invention is to bond components of a flame-retardant product using the moisture-curable composition.
  • flame-retardant products include electrical products, such as speakers, video cassette players, televisions, radios, vending machines, refrigerators, personal computers, card-type batteries, video cameras, and other automotive parts and precision equipment. Can be mentioned.
  • the bonding method of the present invention can also be applied to bonding of high-voltage components, circuits that can be subjected to high voltage and components used in the vicinity thereof, and bonding in electric appliances that are continuously operated for a long time.
  • these components include connectors, switches, relays, electric cables, flyback transformers, deflection yokes, and the like.
  • the remaining mixed solution was gradually added dropwise using a dropping funnel over 3 hours to carry out polymerization.
  • the polymerization was terminated when no exotherm was observed.
  • the number average molecular weight was 970, the polymerization conversion was 9.9%, and the resin solid content was 70%.
  • Each component was mixed in a planetary mixer with the composition shown in Table 1 (unit: parts by weight), mixed at 100 ° C for 1 hour, cooled to 20 ° C, and the curing catalyst and adhesive were added. The resulting mixture was mixed under reduced pressure for 10 minutes to obtain a room-temperature curable composition for each composition.
  • Hydrite H21 Trade name of aluminum hydroxide (average particle size: 25 m) [manufactured by Showa Denko KK].
  • Hygirite H42 Trade name of aluminum hydroxide (average particle size l / _im)
  • Hakuenka CCR Calcium carbonate surface-treated with fatty acids (Shiraishi Calcium Co., Ltd.)
  • Whiteton SB Trade name of calcium carbonate [manufactured by Shiraishi Calcium Co., Ltd.].
  • AEROSIL R 9 7 2 Trade name of silica (manufactured by Nippon AEROSIL)
  • SH620 A trade name of an adhesion-imparting agent [2- (aminoethyl) aminopropyltrimethoxysilane] [manufactured by Toray Industries, Inc.].
  • Adhesive strength Apply each adhesive to mild steel plate (1.6 x 25 x 100 mm) with a bonding area of 25 x 25 mm to a thickness of 200 m, and open time by 3 m. Then, cure at 20 ° C for 7 days and measure the adhesive strength at a pulling speed of 50 mm / 'min.
  • a sheet is made using an adhesive and a 1.5 mm spacer between the silicone release papers. After 7 days at 20 ° C, peel off the release paper to prepare cured sheets of 1.5 x 13 x 13 mm for Examples 2 to 4 and Comparative Examples 1 and 2.
  • Example 1 after curing with a dryer at 70 ° C. for 7 days, a cured sheet of 1.5 ⁇ 13 ⁇ 130 mm is produced. Adjust a 9.5 mm inner diameter Bunsempana into a blue flame with a flame height of 19 mm, and indirectly flame 10 seconds into the center of the lower end of the test specimen, whose length is held vertically by a clamp. As soon as combustion stops after contact with the flame, apply the flame again to the same spot on the specimen for 10 seconds. Record the first and second burn times.
  • the adhesive was filled in a 135 ml laminating tube, allowed to stand at 23 ° C. for 90 days and at 50 ° C. for 60 days, and a bleeding liquid was observed.
  • FIG. 1 is a perspective explanatory view showing the structure of the deflection yoke and the locations where the adhesive is applied.
  • reference numeral 10 denotes a deflection yoke, which has a bobbin 20.
  • a wedge 22 protruding laterally is provided on the lower surface of the bobbin 20.
  • Reference numeral 24 denotes a coil mounted on the upper surface of the bobbin 20.
  • a ferrite 25 is attached to the coil 24.
  • a purity magnet 30, a 4-pole converter-sense magnet 32, and a 6-pole convergence magnet 34 are stacked and mounted via a mounting plate 28 provided with a deflection yoke tightening screw 26. .
  • the assembly of the deflection yoke 10 is performed as follows. After the tentative assembly of the pobin 20, ferrite 25 and coil 24 without using an adhesive, they are bonded to each other with an adhesive. Next, the magnets 30, 32, 34, silicon steel plate parts, and SUS parts are bonded to the pobin 20 with an adhesive. Finally, the deflection yoke 10 is temporarily fixed to a cathode ray tube (not shown) using wedges 22 and then bonded with an adhesive.
  • the location where the adhesive is applied is the next location as shown in FIG.
  • Hot-melt adhesives softened at high temperatures, sometimes causing parts to shift.
  • rubber-based adhesive contains a solvent as a composition, it may cause occupational safety and health problems, environmental pollution, and also may cause plastic parts to be damaged due to stress cracking.
  • Silicone RTV has good heat resistance and is solvent-free, but it has basically had a problem of poor adhesion to various adherends.
  • 4Since epoxy adhesives can be cured at room temperature, two-pack type is usually used.However, incorrect measurement of the base resin curing agent, poor yield, and curing at room temperature only In some cases, the length of the curing time in the case where the heat treatment was performed was pointed out.
  • the moisture-curable composition of the present invention is applied as an adhesive instead of the conventional various adhesives having the above-mentioned problems, the problems of the conventional adhesive can be solved at once. That is, the moisture-curable composition of the present invention is flame-retardant, can be made solvent-free, does not soften at high temperatures, has good adhesion to various adherends, and has excellent storage stability. Of course, it can be used as an ideal adhesive because it does not have the problems of conventional adhesives as well as can be used as a substitute for conventional adhesives. Industrial applicability
  • the moisture-curable adhesive of the present invention is flame-retardant, easily solvent-free, does not soften at high temperatures, has good adhesion to various adhesives, and has excellent storage stability. Therefore, it has an effect that it can be suitably used as an adhesive or a fixing agent for assembling electric products or precision equipment requiring flame retardancy.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

Composition durcissable à l'humidité ayant d'excellentes performances requises pour des adhésifs ou des fixateurs destinés à être utilisés dans l'assemblage d'appareils électriques ou de précision pour lesquels des propriétés ignifuges sont requises. La composition comprend comme ingrédients essentiels (A) au moins un polymère choisi dans le groupe constitué d'un polymère de polyuréthane ayant un groupe réactif réticulable par hydrolyse, d'un polymère (méth)acrylique ayant un groupe réactif réticulable par hydrolyse, d'un silicone ayant un groupe réactif réticulable par hydrolyse et d'un polymère de polyoxyalkylène ayant un groupe réactif réticulable par hydrolyse, (B) un hydroxyde de métal ayant un diamètre moyen des particules de 0,1 à 200 µm et (C) un carbonate de calcium traité en surface ayant un diamètre moyen des particules de 0,01 à 10 µm.
PCT/JP2004/003289 2004-03-12 2004-03-12 Composition durcissable à l'humidité et procédé de collage WO2005087865A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7605203B2 (en) 2005-05-26 2009-10-20 Tremco Incorporated Polymer compositions and adhesives, coatings, and sealants made therefrom
WO2011089987A1 (fr) * 2010-01-20 2011-07-28 コニシ株式会社 Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif
US7994261B2 (en) 2004-06-23 2011-08-09 Tremco, Incorporated Highly elastomeric and paintable silicone compositions
EP2465895A1 (fr) * 2010-12-15 2012-06-20 Merz+Benteli AG Thermodurcissable adhésif, scellement et revêtement
JP2014132100A (ja) * 2014-04-16 2014-07-17 Cemedine Co Ltd 貯蔵安定性に優れる難燃伝熱性硬化性組成物の製造方法

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JPS50156599A (fr) * 1974-06-07 1975-12-17
JPH11209620A (ja) * 1998-01-20 1999-08-03 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JPH11310682A (ja) * 1998-04-30 1999-11-09 Cemedine Co Ltd 湿気硬化型組成物
JP2001002746A (ja) * 1999-06-22 2001-01-09 Asahi Chem Ind Co Ltd 無機変性ポリウレタンエマルジョン
JP2003226854A (ja) * 2002-02-04 2003-08-15 Toagosei Co Ltd 接着剤組成物
JP2003313397A (ja) * 2002-04-24 2003-11-06 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2004059851A (ja) * 2002-07-31 2004-02-26 Dainippon Ink & Chem Inc 熱伝導電気絶縁感圧接着剤用組成物、およびこれを用いた粘着シート

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JPS50156599A (fr) * 1974-06-07 1975-12-17
JPH11209620A (ja) * 1998-01-20 1999-08-03 Shin Etsu Chem Co Ltd 室温硬化性オルガノポリシロキサン組成物
JPH11310682A (ja) * 1998-04-30 1999-11-09 Cemedine Co Ltd 湿気硬化型組成物
JP2001002746A (ja) * 1999-06-22 2001-01-09 Asahi Chem Ind Co Ltd 無機変性ポリウレタンエマルジョン
JP2003226854A (ja) * 2002-02-04 2003-08-15 Toagosei Co Ltd 接着剤組成物
JP2003313397A (ja) * 2002-04-24 2003-11-06 Kanegafuchi Chem Ind Co Ltd 硬化性組成物
JP2004059851A (ja) * 2002-07-31 2004-02-26 Dainippon Ink & Chem Inc 熱伝導電気絶縁感圧接着剤用組成物、およびこれを用いた粘着シート

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7994261B2 (en) 2004-06-23 2011-08-09 Tremco, Incorporated Highly elastomeric and paintable silicone compositions
US7605203B2 (en) 2005-05-26 2009-10-20 Tremco Incorporated Polymer compositions and adhesives, coatings, and sealants made therefrom
WO2011089987A1 (fr) * 2010-01-20 2011-07-28 コニシ株式会社 Composition de résine ignifuge durcissable à l'humidité, agent adhésif ignifuge durcissable à l'humidité comprenant ladite composition, et procédé de collage utilisant ledit agent adhésif
EP2465895A1 (fr) * 2010-12-15 2012-06-20 Merz+Benteli AG Thermodurcissable adhésif, scellement et revêtement
JP2014132100A (ja) * 2014-04-16 2014-07-17 Cemedine Co Ltd 貯蔵安定性に優れる難燃伝熱性硬化性組成物の製造方法

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