JP4447868B2 - Curable adhesive composition - Google Patents

Description

The present invention relates to improved relates curable adhesive composition, particularly workability relates curable adhesive composition less simultaneously excellent adhesion and heat resistance toxicity, particularly adhesion to hard-to-bond materials such as polyolefin materials The present invention relates to a curable adhesive composition that is suitably used as an adhesive.

  Various types of polyolefin materials such as polyethylene (PE), polypropylene (PP), and polyolefin copolymers such as ethylene propylene terpolymer (EPDM) or mixed molded articles containing any of these polyolefin materials Although there has been demand in the field, in recent years, it has become clear that vinyl chloride resins that have been used so far generate hydrogen chloride gas during incineration, which is unfavorable for the environment. Polyolefin materials are being studied and their demand is growing rapidly. Polyolefin materials are recyclable and safer materials, but have a problem of poor adhesion in adhesion or painting.

As adhesives used for polyolefin materials, adhesives for polyolefins such as urethane, polyester, and aqueous acrylic emulsion systems have been proposed so far, but sufficient adhesive strength can be obtained even if these adhesives are used. No. In addition, in order to enhance adhesion in polyolefin materials or coating, methods of surface treatment such as chemical treatment with strong acid or strong alkali, primer treatment, corona treatment, reduced pressure plasma treatment, UV treatment, laser irradiation treatment, etc. have been studied. However, all have problems such as toxicity and poor workability, adhesion or heat resistance.
JP 50-156599 A JP-A-52-73998 JP-A-62-230822 JP-A-60-228516 Japanese Unexamined Patent Publication No. Sho 63-112642 JP-A-1-131271 JP 55-9669 A JP 59-122541 A Japanese Unexamined Patent Publication No. 60-6747 JP-A-61-233043 JP-A-3-79627 JP-A-4-283259 JP-A-5-70531 JP-A-5-287186 Japanese Patent Laid-Open No. 11-80571 Japanese Patent Laid-Open No. 11-116763 JP-A-11-130931 Japanese Patent Laid-Open No. 11-80571 Japanese Patent Application Laid-Open No. 11-100197 JP 2000-143757 A JP 2000-169544 A JP 2002-212415 A Japanese Patent No. 3030020 Japanese Patent No. 3295663 Japanese Patent No. 3313360 Japanese Patent No. 3317353 Japanese Patent No. 3350011 JP 59-78223 A Japanese Examined Patent Publication No. 2-42367

The present invention provides workability, adhesion and less at the same time toxic when excellent heat resistance, preferably curable adhesive composition for use in particular as an adhesive with improved adhesion to hard-to-bond materials such as polyolefin materials The purpose is to do.

In order to solve the above problems, the curable adhesive composition of the present invention comprises (A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group, (B) 10 to 400 parts by weight of a tackifier, (C) An oxyalkylene polymer containing 10 to 200 parts by weight of an acrylic polymer and (D) 0.1 to 20 parts by weight of a curing catalyst , wherein (A) has a hydrolyzable silicon-containing functional group. Or a composition comprising an oxyalkylene polymer having a hydrolyzable silicon-containing functional group and a (meth) acrylic acid (co) polymer.
The method for producing an adhesive of the present invention comprises (A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group, (B) 10 to 400 parts by weight of a tackifier, and (C) 10 to 10 parts of an acrylic polymer. 200 parts by weight and (D) a method for producing an adhesive using a curable composition containing 0.1 to 20 parts by weight of a curing catalyst, wherein (A) comprises a hydrolyzable silicon-containing functional group. It is a composition comprising an oxyalkylene polymer having a hydrolyzable silicon-containing functional group and a (meth) acrylic acid (co) polymer.

  As said (A), the oxyalkylene polymer which has a silicon-containing functional group which can be bridge | crosslinked by forming a siloxane bond can be used.

  As the above (A), it is preferable to use a composition comprising an oxyalkylene polymer having a silicon-containing functional group that can be crosslinked by forming a siloxane bond and a (meth) acrylic acid (co) polymer.

  The (B) is preferably a styrene (co) polymer.

  As said (C), the acrylic (co) polymer which superposed | polymerized 1 or more types of acrylic acid ester is used suitably.

  The above (D) is preferably a silanol condensation catalyst.

It is preferable to further add (E) an epoxy resin to the curable adhesive composition.

According to the present invention, workability, adhesion and less at the same time toxic when excellent heat resistance, particularly suitable for curing the adhesive composition used as an adhesive with improved adhesion to hard-to-bond materials such as polyolefin materials Can be provided.

  Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.

Curable adhesive composition of the present invention, the following components (A), (B), a curable adhesive composition containing the (C) and (D).
(A) Polymer having hydrolyzable silicon-containing functional group (B) Tackifier (C) Acrylic polymer (D) Curing catalyst

In the present invention, (A) The polymer having a hydrolyzable silicofluoride-containing functional group used as the component, conventionally available widely known ones, such as proposed in Patent Documents 1 to 3 and the like molecules oxyalkylene polymer having hydrolyzable silicofluoride-containing functional groups in the non-end, oxyalkylene having silicofluoride-containing functional group capable of crosslinking by forming a proposed such a siloxane bond in Patent Document 4 to 6, etc. The composition etc. which consist of a polymer and a (meth) acrylic acid (co) polymer can be mentioned. Particularly proposed in Patent Document 4 to 6 or the like, the oxyalkylene polymer and (meth) acrylic acid (co) consisting of polymer composition having a silicofluoride-containing functional group capable of crosslinking by forming a siloxane bond adhesive It is preferable in terms of characteristics.

Further, the polymer having the hydrolyzable silicofluoride-containing functional group as (A), for example, may be mentioned those disclosed in the patent literature 1 to 27. Specific examples of polymers having a hydrolyzable silicofluoride-containing functional group (A) in the present invention contains one or more crosslinkable silyl groups in the molecule, the main chain respectively containing organosiloxane Polyoxyalkylene polymer, vinyl-modified polyoxyalkylene polymer, vinyl polymer, polyester polymer, acrylate polymer, methacrylic acid ester polymer, copolymers and mixtures thereof, etc. Can be mentioned. It is preferable that 1-5 crosslinkable silyl groups are contained in a molecule | numerator from points, such as the sclerosis | hardenability of a sealing material, and the physical property after hardening. Furthermore, the crosslinkable silyl group is preferably one represented by the following general formula (1) which is easily crosslinked and easy to produce.

Wherein R is a hydrocarbon group, preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms, and most preferably a methyl group. The reactive group is a group selected from a halogen atom, a hydrogen atom, a hydroxyl group, an alkoxy group, an acyloxy group, a ketoximate group, an amide group, an acid amide group, a mercapto group, an alkenyloxy group, and an aminooxy group. In this case, X may be the same group or different groups, among which X is preferably an alkoxy group, most preferably a methoxy group, a is an integer of 0, 1 or 2, Most preferred.)

The main chain of the polymer (A) having a hydrolyzable of silicofluoride-containing functional groups, tensile adhesion after curing, in terms of the physical properties of the modulus or the like may also contain organosiloxane, polyoxyalkylene Polymers and / or vinyl-modified polyoxyalkylene polymers are preferred, and polyoxypropylene polymers, acrylic-modified polyoxypropylene polymers, and / or methacryl-modified polyoxypropylene polymers that may contain an organosiloxane. Further preferred.

  The vinyl-modified polyoxyalkylene polymer which may contain an organosiloxane containing one or more crosslinkable silyl groups in the molecule contains one or more crosslinkable silyl groups in the molecule. In the presence of a polyoxyalkylene polymer which may contain an organosiloxane, one or more vinyl monomers are added by a normal radical polymerization method such as addition of a radical polymerization initiator or ultraviolet irradiation. It can obtain by making it superpose | polymerize etc. (patent documents 28 and 29 etc. are mentioned as a reference, However, It is not limited to these).

  The vinyl monomer is a compound having one or more polymerizable unsaturated bonds in the molecule, for example, ethylene, propylene, isobutylene, butadiene, chloroprene, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid. , Vinyl acetate, acrylonitrile, styrene, chlorostyrene, 2-methylstyrene, divinylbenzene, methyl acrylate, ethyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate, benzyl acrylate, glycidyl acrylate , Methyl methacrylate, ethyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, benzyl methacrylate, glycidyl methacrylate, acrylamide, methacrylate Amides, n-methylol acrylamide, ethoxylated phenol acrylate, ethoxylated paracumyl phenol acrylate, ethoxylated nonyl phenol acrylate, propoxylated nonyl phenol acrylate, 2-ethylhexyl carbitol acrylate, N-vinyl-2-pyrrolidone, isobornyl acrylate, ethoxy Bisphenol F diacrylate, ethoxylated bisphenol A diacrylate, ethoxylated isocyanuric acid diacrylate, tripropylene glycol diacrylate, pentaerythritol diacrylate monostearate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, pentaerythritol triacrylate, tri Methylolpropane triacre relay , Ethoxylated isocyanuric acid triacrylate, propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, polyurethane di Acrylate, ω-carboxy-polycaprolactone monoacrylate, phthalic acid monohydroxyethyl acrylate, acrylic acid dimer, 2-hydroxy-3-phenoxypropyl acrylate, polyester polyacrylate, 1,6-hexanediol diacrylate, 2- (2- Ethoxyethoxy) ethyl acrylate, stearyl acrylate, tetrahydroph Furyl acrylate, lauryl acrylate, 2-phenoxy acrylate, isodecyl acrylate, isooctyl acrylate, tridecyl acrylate, caprolactone acrylate, zinc diacrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, diethylene glycol di Acrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, propoxylated glycerin triacrylate, ethoxylated pentaerythritol tetraacrylate, pentaacrylate ester, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate , Lauryl methacrylate Polypropylene glycol dimethacrylate, triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, diethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate , Neopentyl glycol dimethacrylate, 1,3-butanediol dimethacrylate, ethoxylated bisphenol A dimethacrylate, zinc dimethacrylate, trimethylolpropane trimethacrylate, and compounds represented by the following chemical formulas (2) to (25) However, it is not limited to these.

  The vinyl monomer is used in an amount of 0.1 to 1000 parts by weight, more preferably 1 to 200 parts by weight, based on 100 parts by weight of the polyoxyalkylene polymer which may contain an organosiloxane. preferable. The vinyl-modified polyoxyalkylene polymer containing one or more crosslinkable silyl groups in the molecule and optionally containing an organosiloxane contains one or more crosslinkable silyl groups in the molecule. A crosslinkable silyl group obtained by introducing a crosslinkable silyl group into a polymer obtained by polymerizing one or more of the above-mentioned vinyl monomers and a polyoxyalkylene polymer which may contain an organosiloxane. A blend of the group-containing vinyl polymer can also be used.

In the present invention, the number average molecular weight of the polymer having hydrolyzable silicofluoride-containing functional group (A) is 1,000 or more, easy to handle particularly narrow molecular weight distribution from 6,000 to 30,000 is because a low viscosity before curing, Properties such as strength, elongation and modulus after curing are suitable. The said component (A) may be used only by 1 type, and may be used together 2 or more types.

  Examples of the tackifier as the component (B) include, for example, styrene (co) polymers; coumarone resins such as coumarone-indene resin, coumarone resin mixed with naphthene resin, phenol resin, rosin and the like; pt-Butylphenol-acetylene resin, phenol formaldehyde resin with low polymerization degree and low softening point (about 60-100 ° C), xylene-phenol resin, xylene resin, terpene that improves not only adhesiveness but also adhesion and heat resistance -Phenol resins such as phenol resins and terpene resins, terpene resins; synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, petroleum hydrocarbons such as hydrogenated hydrocarbon resins Hydrogen resin; rosin, rosin pentaerythritol ester, rosin glycero・ Ester, hydrogenated rosin, highly hydrogenated wood resin, hydrogenated rosin methyl ester, hydrogenated rosin triethylene glycol ester, hydrogenated rosin pentaerythritol ester, polymerized rosin, polymerized rosin glycerol ester, Examples include, but are not limited to, rosin derivatives such as zinc resinate and hardened rosin; low molecular weight polystyrene, and other special preparations. Of these, styrene polymers and / or styrene copolymers are particularly preferred. These tackifiers may be used alone or in combination of two or more. The blending ratio of the component (B) is preferably 10 to 400 parts by weight, more preferably 30 to 300 parts by weight, still more preferably 50 to 200 parts by weight with respect to 100 parts by weight of the component (A). It is. Specifically, when (E) epoxy resin is not added, it is preferable to use 30 to 150 parts by weight of component (B) with respect to 100 parts by weight of component (A), and (E) epoxy resin is added. In that case, it is preferable to use 70 to 200 parts by weight.

  As the styrene-based (co) polymer, conventionally known polymers can be widely used, and are not particularly limited. For example, styrene-based polymers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and salts thereof. (Co) polymer obtained by (co) polymerizing 1 or more types of monomers is mentioned. Specific examples of the styrenic polymer include trade names: FTR-8100 and FTR-8120 manufactured by Mitsui Chemicals, Inc. In addition, as the styrene copolymer, a copolymer obtained by copolymerizing one or more styrene monomers and one or more other monomers copolymerizable therewith may be used. Is possible. The copolymerizable monomer is not particularly limited, and examples thereof include α-olefins having 2 to 12 carbon atoms such as 1-heptene, ethyl-1-butene, and methyl-1-nonene; -Unsaturated compounds such as non-conjugated dienes such as pentadiene and dicyclopentadiene. As the styrene copolymer, specifically, trade names: FTR-6100, FTR-6125, FTR-7125, etc., manufactured by Mitsui Chemicals, Inc. can be used. The above styrenic (co) polymers may be used alone or in combination of two or more.

  As the acrylic polymer used as the component (C), conventionally known polymers can be widely used, and are not particularly limited. (Meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide An acrylic (co) polymer obtained by polymerizing one or more selected from acrylic monomers such as the above can be used. Preferable examples include acrylic (co) polymers obtained by polymerizing at least one (meth) acrylic acid ester, and in particular, those containing a (meth) acrylic acid ester monomer as the main component, It is more preferable to use a (meth) acrylic acid ester having 1 to 20 carbon atoms.

  Examples of the (meth) acrylic acid ester having 1 to 20 carbon atoms in the ester moiety include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) Butyl acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, neopentyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic acid Alkyl (meth) acrylates such as isodecyl, lauryl (meth) acrylate, tridecyl (meth) acrylate and stearyl (meth) acrylate; cyclohexyl (meth) acrylate, isobornyl (meth) acrylate and (meth) acrylic acid (Meth) acrylic acid alicyclic alkyl such as tricyclodecynyl; (Hydroxyethyl acrylate), hydroxybutyl (meth) acrylate, hydroxypropyl (meth) acrylate and (meth) acrylic acid hydroxyethyl (meth) acrylate such as ε-caprolactone addition reaction product; (meth) acrylic Heteroatom-containing (meth) acrylic acid esters such as 2-methoxyethyl acid, dimethylaminoethyl (meth) acrylate, chloroethyl (meth) acrylate, trifluoroethyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate Examples include, but are not limited to: Moreover, you may use together 1 type, or 2 or more types of these. Among the above (meth) acrylic acid esters, butyl acrylate, 2-ethylhexyl acrylate and 2-methoxyethyl acrylate are preferred because a polymer having a low glass transition temperature is obtained.

  In addition to the acrylic monomer, the acrylic polymer can be copolymerized with other monomers copolymerizable therewith. Examples of the copolymerizable monomer include vinyl monomers such as α-olefins, vinyl esters, and vinyl ethers.

  The glass transition temperature of the acrylic polymer is 10 ° C. or lower, preferably 0 ° C. or lower, more preferably −10 ° C. or lower. The weight average molecular weight is 500 or more and 20,000 or less, and preferably 700 or more and 10,000 or less. When the glass transition temperature is higher than 10 ° C., workability at low temperatures is deteriorated. On the other hand, when the weight average molecular weight exceeds 20,000, sufficient plasticity is not exhibited and workability is deteriorated. On the other hand, when the weight average molecular weight is less than 500, the low molecular weight polymer bleeds, resulting in a decrease in contamination. Component (C) is preferably used in an amount of 10 to 200 parts by weight, more preferably 40 to 100 parts by weight, based on 100 parts by weight of component (A). The said acrylic polymer may be used independently and may be used together 2 or more types.

  The (D) curing catalyst is not particularly limited as long as it exhibits the effect of the curing catalyst on the component (A), but a silanol condensation catalyst is preferably used. Examples of the silanol condensation catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate: octylic acid Lead; butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, Diphenylguanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-di Amine compounds such as zabicyclo (5.4.0) undecene-7 (DBU) or salts thereof with carboxylic acid, etc .; low molecular weight polyamide resin obtained from excess polyamine and polybasic acid; excess polyamine and epoxy Reaction products with compounds: Known silanol condensation catalysts such as silane coupling agents having amino groups such as r-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. (D) When using a silanol condensation catalyst as a component, it is preferable to use 0.1-20 weight part of compounding ratios of a silanol condensation catalyst with respect to 100 weight part of component (A). These curing catalysts may be used alone or in combination of two or more.

It is preferable to further add (E) an epoxy resin to the curable adhesive composition of the present invention. As the (E) epoxy resin, conventionally known epoxy resins can be widely used, and are not particularly limited, but it is preferable to use a bisphenol type epoxy resin or an epoxy resin having a polyoxyalkylene skeleton. The epoxy resin having a polyoxyalkylene skeleton is not particularly limited as long as it has a polyoxyalkylene structure, but bisphenol A, bisphenol F, bisphenol AD, and an epoxy resin having a polyoxyalkylene unit including novolac and the like. A more preferable example is given.

  The blending ratio of the (E) epoxy resin is preferably 5 to 200 parts by weight, more preferably 30 to 150 parts by weight with respect to 100 parts by weight of the component (A). This epoxy resin may be used independently and may use 2 or more types together.

  (E) When adding an epoxy resin, a curing agent (epoxy resin curing agent) for the epoxy resin is added. As the epoxy resin curing agent, commonly used curing agents for epoxy resins can be used, and are not particularly limited. For example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperacin , M-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amines such as 2,4,6-tris (dimethylaminomethyl) phenol; tertiary amine salts; polyamide resins; imidazole Ketimines; Dicyandiamides; Boron trifluoride complexes; phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride , Carboxylic anhydrides such such as anhydrous Kuroren acid; and the compound of the carboxylic acids and the like; alcohols; phenols. Although the usage-amount of the said hardening | curing agent changes with kinds of an epoxy resin and a hardening | curing agent, what is necessary is just to use a hardening | curing agent suitably for the objective in the range of 0.1-300 parts with respect to 100 weight part of epoxy resins. These curing agents may be used alone or in combination of two or more. Of course, it is possible to use a curing catalyst for the component (A) and a curing agent for the epoxy resin as the curing catalyst (D) and the curing agent.

The curable adhesive composition of the present invention includes a filler, a plasticizer, an adhesion-imparting agent, a stabilizer, a wax, an anti-aging agent, as necessary, in order to adjust the viscosity and physical properties in addition to the components described above. Various additives such as an ultraviolet absorber, a light stabilizer, a thixotropic agent, and a colorant can be blended.

  The plasticizer is not particularly limited as long as it is a process oil or other hydrocarbon compatible with the polymer, and various known plasticizers can be used. For example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyls; hydrocarbon oils such as partially hydrogenated terphenyls; Process oils; alkylbenzenes and the like.

  Examples of the filler include normal calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste range, glass balloon, vinylidene chloride resin balloon, acrylonitrile / methacrylonitrile resin balloon. Can be used alone or in combination.

  A silane coupling agent or the like is used as an adhesion-imparting agent, and a hindered phenol compound or a triazole compound is used as a stabilizer. Examples of the colorant include titanium white, carbon black, and bengara.

The curable adhesive composition of the present invention can be a one-component type or a two-component type as required.

According to the present invention, it is possible to obtain a curable adhesive composition having excellent adhesion to not only metal, glass and painted surfaces but also polyolefin materials for which good adhesion has not been obtained so far. In the curable adhesive composition of the invention, the adherend is not only a metal / glass / painted surface, but also a polyolefin copolymer such as polyethylene (PE), polypropylene (PP), ethylene propylene terpolymer (EPDM) or the like. In the case of a polyolefin material such as a mixed molded body containing any of these polyolefin materials, the utility is great in joining the same kind of material and joining these different materials.

Since the curable adhesive composition of the present invention exhibits good adhesion to many substrates, adhesives, joint materials, sealing materials, waterproofing materials, paint / coating materials, lining materials, sealing materials, It can be used as a pressure-sensitive adhesive tape, a pressure-sensitive adhesive sheet, a pressure-sensitive adhesive, a pressure-sensitive adhesive processed product, and the like.

When used as an adhesive, the curable adhesive composition of the present invention has excellent rubber elasticity and adhesion durability, balance between shear strength and peel strength, and hot strength. Between different types of substrates with different thermal expansion coefficients, such as bonding of precision equipment parts, wood flooring, bonding between glass, decorative board, mirror, design panel, ceramic panel, etc., concrete, PC concrete, cement, etc. Bonding, stone materials, foamed moldings, glass, mirrors, inorganic porous substrates, ceramic tiles, and other materials with weak surface strength, and bonding between these materials and other substrates, adhesion of large panels, waterproof sheets, Adhesion that requires high durability such as adhesion of water-absorbent sheets; Adhesion of materials with low solvent resistance such as organic foam; Lamination for packaging and cosmetics using plastics film, paper, aluminum foil, PVC sheet, etc. Adhesives, adhesives that require high peel strength such as vinyl tiles, carpets, and plastic sheets, adhesives for difficult-to-adhere materials such as FRP, silicone rubber, unvulcanized rubber, and engineering plastics, adhesives for ceramic tiles and panels, automobiles Adhesives for vehicle hemming and well bonding, adhesives for SMC, adhesives between the cores of honeycomb panels such as steel plates and aluminum, between panels and between cores and outer frames, adhesives for jointing and raising concrete , Adhesion of steel for concrete repair and reinforcement, Adhesive for fixing anchor bolts to concrete, Adhesive for PC block method, Adhesion between segment concrete such as tunnels, Adhesion of fuse pipes and PVC pipe joints for water and sewage , Low temperature insulation foam adhesive, motor and speaker ferrite and core, and ferrite and metal plug Over bets adhesion, adhesion of lenses and prisms can be used for adhesion or the like to the optical fiber connection connector.

  As a sealing material, it can be used for primary and secondary sealing of siding boats, sealing of brake lamps and headlamps, and the like.

  As a waterproofing material / flooring material, it can be used as a waterproofing coating material / paving material / flooring material / athletic material. As a paint / coating, in addition to an elastic paint, it can be used as a waterproofing coat for segment concrete, an antifouling paint, and a ship bottom paint. It can also be used as a putty for repairing cracked concrete and collapsed parts. As a lining material, it can also be used as an anticorrosion lining for concrete, steel plates, reinforcing bars, etc. As a sealing material, it can be used as a sealing material for circuits such as LSI and LEDs.

  The base material that can be used in these applications is not particularly limited. For example, glass, aluminum, rolled steel sheet, stainless steel sheet, zinc-treated steel sheet, chromic acid-treated steel sheet, phosphoric acid-treated steel sheet, plated steel sheet, Tin plate, cast forged products, copper plate, brass plate, zinc plate, etc., coated steel plate treated with organic paint or inorganic paint such as epoxy, acrylic, polyester, etc., plastic sheet such as soft PVC, fluorine polymer, PET Laminated steel sheet, hollow panel, woodworking material, plastics such as vinyl chloride, styrene, acrylic, ABS, bakelite, PET, PBT, polycarbonate, nylon, polyimide, polyarylate, foamed styrene, foamed urethane, PVC foam・ Foamed molded products such as inorganic foam, FRPs, NR / NBR / Si / unvulcanized Rubber such as rubber, concrete such as paper, PC concrete, stone such as natural stone / artificial marble, ALC, mortar, asbestos slate, gypsum board / calcal board, cement, fiber reinforced cement, ceramic tile An inorganic porous substrate such as can be exemplified.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

(Examples 1 to 10 and Comparative Example 1)
Example 1
As shown in Table 1, (A) Silyl MA X- 470 (manufactured by Kaneka Chemical Co., Ltd.), Silyl SAX-220 (Kanban Chemical Industry (as a polymer having a hydrolyzable silicon-containing functional group) ( 50 parts by weight, 30 parts by weight and 20 parts by weight of MS polymer S-203H (manufactured by Kaneka Chemical Co., Ltd.), respectively, and (B) FTR-8120 (styrene heavy weight) as a tackifier Combined: Mitsui Chemicals Co., Ltd.): 90 parts by weight, and (C) UP-1000 (manufactured by Toagosei Co., Ltd.): 40 parts by weight as an acrylic polymer, and after heating and melting, D) SCAT-25 as a curing catalyst (dibutyltin diacetylacetate: manufactured by Sansha Co., Ltd.): 4 parts by weight, and KBM-603 (N-β (aminoethyl) γ-aminopropyl) which is a silane coupling agent Trimethoxysilane: Shin-Etsu Chemical Co., Ltd.): 4 parts by weight and the curable composition were added respectively to prepare.

The amount of each compounding substance in Table 1 is shown in parts by weight, and Note 1) to Note 14) are as follows.
* 1: Trade name: Silyl MA X- 470 (polymer having hydrolyzable silicon-containing functional group: manufactured by Kaneka Chemical Co., Ltd.)
* 2: Trade name; Silyl SAX-220 (polymer having hydrolyzable silicon-containing functional group: manufactured by Kaneka Chemical Co., Ltd.)
* 3: Trade name; MS polymer S-203H (polymer having hydrolyzable silicon-containing functional group: manufactured by Kaneka Chemical Co., Ltd.)
* 4: Product name: FTR-8120 (styrene polymer: manufactured by Mitsui Chemicals, Inc.)
* 5: Product name: FTR-7125 (styrene copolymer: manufactured by Mitsui Chemicals, Inc.)
* 6: Product name; FTR-6125 (styrene copolymer: manufactured by Mitsui Chemicals, Inc.)
* 7: Product name: UP-1000 (manufactured by Toagosei Co., Ltd.)
* 8: Product name; Adeka Resin EP-4000 (Bisphenol alkylene oxide-added epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.)
* 9: Product name: Adekaglycilol ED-506 (polyalkylene glycol type epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.)
* 10: Product name; Adeka Resin EPU-16A (Bisphenol alkylene oxide-added epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.)
* 11: Product name: Adeka Resin EP-4100 (Bisphenol A type epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.)
* 12: Product name; SCAT-25 (dibutyltin diacetylacetate: manufactured by Sansha Co., Ltd.)
* 13: Product name: Versamine EH-30 (2,4,6-tris (dimethylaminomethyl) phenol: manufactured by Cognis Japan Co., Ltd.)
* 14: Product name: KBM-603 (N-β (aminoethyl) γ-aminopropyltrimethoxysilane: manufactured by Shin-Etsu Chemical Co., Ltd.)

(Example 2)
As shown in Table 1, as component (A), 50 parts by weight, 30 parts by weight and 20 parts by weight of Silyl MA X- 470, Silyl SAX-220 and MS polymer S-203H were blended as component (B). FTR-7125 (styrene copolymer: manufactured by Mitsui Chemicals, Inc.): 90 parts by weight and UP-1000: 40 parts by weight as component (C) were mixed and heated to melt, and then component (D) SCAT-25: 4 parts by weight and KBM-603: 4 parts by weight as a silane coupling agent were added to prepare a curable composition.

(Example 3)
As shown in Table 1, as component (A), 50 parts by weight, 30 parts by weight and 20 parts by weight of Silyl MA X- 470, Silyl SAX-220 and MS polymer S-203H were blended as component (B). FTR-6125 (styrene copolymer: manufactured by Mitsui Chemicals, Inc.): 90 parts by weight and UP-1000: 40 parts by weight as component (C) were mixed and heated to melt, and then component (D) SCAT-25: 4 parts by weight and KBM-603: 4 parts by weight as a silane coupling agent were added to prepare a curable composition.

Example 4
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 110 parts by weight, UP-1000 as the component (C) : 45 parts by weight, and Adeka Resin EP-4000 (bisphenol alkylene oxide-added epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.) as component (E): 10 parts by weight were mixed and heated to melt, and then component (D) SCAT-25: 4 parts by weight, silane coupling agent KBM-603: 4 parts by weight, and epoxy resin curing agent Versamine EH-30 (2,4,6-tris (dimethylaminomethyl) phenol: Cognis Japan ( Co., Ltd.): 1 part by weight was added to prepare a curable composition.

(Example 5)
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 135 parts by weight, UP-1000 as the component (C) : 55 parts by weight, and Adeka Resin EP-4000: 35 parts by weight as component (E) were respectively melted by heating, and then SCAT-25: 4 parts by weight as component (D), KBM- which is a silane coupling agent A curable composition was prepared by adding 603: 4 parts by weight and Versamine EH-30: 3.5 parts by weight as an epoxy resin curing agent.

(Example 6)
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 170 parts by weight, UP-1000 as the component (C) : 70 parts by weight, and Adeka Resin EP-4000: 70 parts by weight as component (E) were mixed and heated to melt, and then SCAT-25: 4 parts by weight as component (D), KBM- which is a silane coupling agent A curable composition was prepared by adding 603: 4 parts by weight and Versamine EH-30: 7 parts by weight as an epoxy resin curing agent.

(Example 7)
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 170 parts by weight, UP-1000 as the component (C) : 70 parts by weight, and Adeka Resin EP-4000: 100 parts by weight as component (E) were mixed and heated and melted, and then SCAT-25: 4 parts by weight as component (D), KBM- which is a silane coupling agent A curable composition was prepared by adding 603: 4 parts by weight and Versamine EH-30: 10 parts by weight as an epoxy resin curing agent.

(Example 8)
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 170 parts by weight, UP-1000 as the component (C) : 70 parts by weight and, as component (E), ADEKA GLYCIROL ED-506 (polyalkylene glycol type epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.) ) SCAT-25: 4 parts by weight, silane coupling agent KBM-603: 4 parts by weight, and epoxy resin curing agent Versamine EH-30: 7 parts by weight were added to prepare a curable composition. .

Example 9
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 170 parts by weight, UP-1000 as the component (C) : 70 parts by weight, and as component (E), Adeka Resin EPU-16A (bisphenol alkylene oxide-added epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.): 70 parts by weight were respectively mixed and heated and melted, and then as component (D) A curable composition was prepared by adding 4 parts by weight of SCAT-25, 4 parts by weight of KBM-603 as a silane coupling agent, and 7 parts by weight of Versamine EH-30 as an epoxy resin curing agent.

(Example 10)
As shown in Table 1, Silyl MA X -470 and Silyl each 50 parts by weight of SAX-220, FTR-8120 as the component (B) as component (A): 170 parts by weight, UP-1000 as the component (C) : 70 parts by weight, and Adeka Resin EP-4100 (bisphenol A type epoxy resin: manufactured by Asahi Denka Kogyo Co., Ltd.) as component (E): 70 parts by weight were respectively mixed and heated to melt, and then SCAT as component (D) -25: 4 parts by weight, KBM-603 as a silane coupling agent: 4 parts by weight, and Versamine EH-30: 7 parts by weight as an epoxy resin curing agent were added to prepare curable compositions.

(Comparative Example 1)
As shown in Table 1, component (A) as Silyl MA X -470: SCAT 40 parts by weight After stirring formulated respectively, as the component (D): 100 parts by weight, and component (C) as UP-1000 -25: 4 parts by weight and KBM-603: 4 parts by weight as a silane coupling agent were added to prepare curable compositions.

(experimental method)
The curable compositions obtained in Examples 1 to 10 and Comparative Example 1 were each subjected to a 180 degree peel test in accordance with JIS K 6854-2. As shown in Table 2, for rigid adherends, polycarbonate (Mitsubishi Engineering Co., Ltd., trade name: Iupilon NF2000), ABS (Shin-Kobe Electric Co., Ltd., trade name: ABS-N-WN), acrylic Resin (Mitsubishi Rayon Co., Ltd., trade name: Acrylite L # 001), 6-Nylon (Toray Industries, trade name: Amilan CM-1021), FRP (Shin Kobe Electric Co., Ltd., epoxy glass KEL -GEF), HIPS (manufactured by Nisso Resin Co., Ltd., trade name: HPS-H-31171W), PET (manufactured by Tsutsunaka Plastic Co., Ltd., trade name: EPG100), polypropylene (manufactured by Shin-Kobe Electric Machinery Co., Ltd., trade name: PP-N-BN) and polyethylene (EL-N-AN, manufactured by Shin-Kobe Electric Machinery Co., Ltd.) were used, and a PET film was used as the flexible adherend. The thickness of the adhesive was 0.5 mm, the curing was 168 hours, and the pulling speed was 200 mm / min. The results are shown in Table 2. In addition, the numerical value of Table 2 is shown by unit: kgf / 25mm.

  As shown in Table 2, Examples 1 to 10 showed good adhesiveness in any adherend including the hardly adherent adherend, whereas Comparative Example 1 was difficult to adhere. The adhesion to the adherend was poor.

Claims (6)

(A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group,
(B) 10 to 400 parts by weight of a tackifier,
(C) 10 to 200 parts by weight of an acrylic polymer, and (D) 0.1 to 20 parts by weight of a curing catalyst ,
The composition (A) is composed of an oxyalkylene polymer having a hydrolyzable silicon-containing functional group, or an oxyalkylene polymer having a hydrolyzable silicon-containing functional group and a (meth) acrylic acid (co) polymer. curable adhesive composition, characterized in that. The curable adhesive composition according to claim 1, wherein the (B) is a styrene-based (co) polymer. The curable adhesive composition according to claim 1 or 2 , wherein the (C) is an acrylic (co) polymer obtained by polymerizing at least one acrylic ester. Wherein (D) is curable adhesive composition of any one of claims 1-3, characterized in that the silanol condensation catalyst. (E) Epoxy resin is further added, The curable adhesive composition of any one of Claims 1-4 characterized by the above-mentioned.   (A) 100 parts by weight of a polymer having a hydrolyzable silicon-containing functional group,
  (B) 10 to 400 parts by weight of a tackifier,
  (C) 10 to 200 parts by weight of an acrylic polymer, and
  (D) A method for producing an adhesive using a curable composition containing 0.1 to 20 parts by weight of a curing catalyst,
  The composition (A) is composed of an oxyalkylene polymer having a hydrolyzable silicon-containing functional group, or an oxyalkylene polymer having a hydrolyzable silicon-containing functional group and a (meth) acrylic acid (co) polymer. The manufacturing method of the adhesive agent characterized by the above-mentioned.