JP2013155323A - Adhesive - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive, which is capable of fixing adherends to each other instantaneously while also allowing re-positioning of the adherends with respect to each other, has superior processibility such as being capable of being cut into sheets, does not peel off the adherends even when exposed to high temperature environments such as during a fire, and is very excellent in thermal resistance.SOLUTION: An adhesive has tackiness before sintering and has adhesive properties after sintering. The adhesive contains sinterable grains and a polymer component, wherein the polymer component contains a crosslinking structure.

Description

  The present invention relates to an adhesive. Specifically, the present invention relates to a pressure-sensitive adhesive having sinterability, which has adhesiveness before sintering and has adhesiveness after sintering.

  A sinterable adhesive typified by an aqueous dispersion of inorganic particles (for example, see Patent Document 1) does not have tackiness. For this reason, it is difficult to reattach the adherends. In addition, since such a sinterable adhesive requires time and heat treatment from application to fixation, it is difficult to cut out in a sheet shape such as punching.

  On the other hand, an adhesive (see, for example, Patent Document 2) has an advantage that the adherends can be fixed instantaneously. However, when exposed to a high temperature atmosphere such as a fire, the polymer component of the adhesive decomposes. However, there is a problem that it is peeled off from the adherend.

JP 2002-173379 A Japanese Patent Laying-Open No. 2005-082775

  The present invention can fix the adherends instantly, can reattach the adherends, can be cut out in a sheet shape, and is excellent in workability, and in a high-temperature atmosphere such as in a fire. An object of the present invention is to provide an adhesive having excellent heat resistance that does not peel off from an adherend when exposed.

The adhesive of the present invention is
It is an adhesive having adhesiveness before sintering and having adhesiveness after sintering,
Including sinterable particles and a polymer component;
The polymer component has a crosslinked structure.

  In a preferred embodiment, the crosslinkable monomer is contained in a content ratio of 2.0% by weight to 60% by weight in all monomer components constituting the polymer component.

  In a preferred embodiment, the crosslinkable monomer has at least one functional group selected from an acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and an amino group.

  In a preferred embodiment, the yield point of the sinterable particles is 250 ° C to 800 ° C.

  In a preferred embodiment, the sinterable particles are formed from at least one component selected from silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, and phosphorus oxide.

  In a preferred embodiment, the sinterable particles have an average particle size of 0.1 μm to 1000 μm.

  In preferable embodiment, the content rate of the said sinterability particle | grain is 1 weight%-80 weight% with respect to solid content of the said adhesive agent.

  In a preferred embodiment, the polymer component is at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer.

  In preferable embodiment, the adhesive agent of this invention is a sheet form.

  In a preferred embodiment, the adhesive of the present invention has a thickness of 1 μm to 1000 μm.

  According to the present invention, the adherends can be fixed instantaneously, the adherends can be reattached, and the sheet shape can be cut out, and the workability is excellent. It is possible to provide an adhesive having excellent heat resistance that does not peel off from the adherend even when exposed to the bottom.

It is an example of the schematic sectional drawing of the adhesive agent of this invention. It is the schematic of the method for evaluating high temperature adhesiveness and high temperature adhesiveness.

  The adhesive of the present invention has tackiness before sintering and adhesiveness after sintering. Here, the adhesive of the present invention means an adhesive before sintering. That is, the adhesive of the present invention is sticky as it is, and exhibits adhesiveness by sintering.

  “Pressure-sensitive Adhesive” as used in the present invention is a kind of adhesion as defined in JIS, and is a temporary adhesion, which can be adhered only by applying a slight pressure. Say. In addition, since it has cohesive force and elasticity, it adheres strongly, but can be peeled off from a hard smooth surface. An adhesive is a soft solid and does not change state like an adhesive. Since the pressure-sensitive adhesive wets the adherends as they are and resists peeling, when the adherends are bonded together, the adhesive force that can withstand practical use can be instantly exhibited. That is, the pressure-sensitive adhesive has both a liquid property (fluidity) for getting wet to the adherend and a solid property (cohesive force) that resists peeling. Since the pressure-sensitive adhesive is a soft solid, the contact area with the adherend gradually increases by applying pressure or taking time. And since this softness can be maintained for a long time, it has the property of being peeled off when it is desired to peel off.

  The term “adhesive” as used in the present invention refers to the property that the surfaces of the same or different kinds of solids can be bonded and integrated as defined by JIS. The adhesive is a fluid liquid when the adherends are bonded together, and wets and becomes familiar with the adherends. Thereafter, it changes to a solid by heating or chemical reaction, and is firmly bonded at the interface between adherends to exert a force to resist peeling. That is, the adhesive wets with a liquid and adheres with a solid.

  The adhesive of the present invention includes sinterable particles and a polymer component. FIG. 1 is an example of a schematic cross-sectional view of the adhesive of the present invention. In the adhesive 100 of the present invention, the sinterable particles 20 are dispersed in the polymer component 10.

  The content ratio of the sinterable particles in the adhesive of the present invention is preferably 1% by weight to 80% by weight, more preferably 5% by weight to 70%, based on the solid content of the adhesive. % By weight, more preferably 10% by weight to 60% by weight, and particularly preferably 20% by weight to 50% by weight. When the content ratio of the sinterable particles in the adhesive of the present invention falls within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as a fire is sufficiently exhibited. it can.

  The sinterable particles in the adhesive of the present invention preferably include two or more types of sinterable particles having different yield points. When the sinterable particles in the adhesive of the present invention contain two or more kinds of sinterable particles having different yield points, the adhesive of the present invention exhibits even more excellent heat resistance. Can do.

  The yield point of the sinterable particles in the adhesive of the present invention is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C, further preferably 250 ° C to 600 ° C, Especially preferably, it is 250 to 500 degreeC. When the yield point of the sinterable particles in the adhesive of the present invention falls within the above range, the effect of being very difficult to peel off from the adherend even when exposed to a high-temperature atmosphere such as in a fire is sufficiently exhibited. it can.

  Among the two or more types of sinterable particles having different yield points, the yield point of the sinterable particles having the lowest yield point is preferably 250 ° C to 800 ° C, more preferably 250 ° C to 700 ° C. More preferably, it is 250 to 600 ° C, and particularly preferably 250 to 500 ° C. When the yield point of the sinterable particles having the lowest yield point falls within the above range, the adhesive of the present invention can exhibit much more excellent heat resistance.

  Arbitrary appropriate sinterability particle | grains can be employ | adopted as sinterability particle | grains in the adhesive agent of this invention. Such sinterable particles are preferably inorganic particles having sinterability, and more preferably, silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, phosphorus oxide. Sinterable particles formed from at least one component selected from By adopting such sinterable particles, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as in a fire can be sufficiently exhibited.

  The average particle size of the sinterable particles in the adhesive of the present invention is preferably 0.1 μm to 1000 μm, more preferably 0.5 μm to 500 μm, and even more preferably 1 μm to 300 μm, particularly Preferably they are 2 micrometers-150 micrometers. When the average particle diameter of the sinterable particles in the adhesive of the present invention falls within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high temperature atmosphere such as a fire is sufficiently obtained. It can be expressed.

  The polymer component in the adhesive of the present invention has a crosslinked structure. When the polymer component in the adhesive of the present invention has a cross-linked structure, the adhesive of the present invention can exhibit very excellent heat resistance.

  The crosslinked structure can be constructed by any appropriate method. The cross-linked structure is preferably constructed by including a cross-linkable monomer in all monomer components constituting the polymer component. In this case, the content of the crosslinkable monomer in all the monomer components constituting the polymer component is preferably 2.0% by weight to 60% by weight, more preferably 3.0% by weight to 57% by weight. More preferably, the content is 5.0% to 55% by weight, particularly preferably 7.0% to 53% by weight, and most preferably 8.0% to 50% by weight. When the content ratio of the crosslinkable monomer is within the above range, the adhesive of the present invention can exhibit much more excellent heat resistance.

  The crosslinkable monomer may be only one type or two or more types.

  As the crosslinkable monomer, any appropriate crosslinkable monomer can be adopted as long as it is a monomer capable of constructing a crosslinked structure. Such a crosslinkable monomer is preferably a crosslinkable monomer having at least one functional group selected from an acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and an amino group. Specific examples of such a crosslinkable monomer include, for example, a polyfunctional monomer described later.

  The polymer component in the adhesive of the present invention preferably contains an antioxidant. When the polymer component in the adhesive of the present invention contains an antioxidant, the adhesive of the present invention can exhibit much more excellent heat resistance.

  The content of the antioxidant in the adhesive of the present invention is preferably 0.1 wt% to 10 wt%, more preferably 0.3 wt%, based on the solid content of the adhesive. % To 8% by weight, more preferably 0.5% to 6% by weight, and particularly preferably 0.7% to 5% by weight. When the content ratio of the antioxidant falls within the above range, the adhesive of the present invention can exhibit much more excellent heat resistance. The antioxidant may be only one kind or two or more kinds.

  Any appropriate antioxidant can be adopted as the antioxidant. As such an antioxidant, Preferably, at least 1 sort (s) chosen from a phenolic antioxidant, an amine antioxidant, an aminoether antioxidant, and a phosphorus antioxidant is mentioned.

Examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrenated mixed cresol, DL-α-tocopherol, steari monocyclic phenolic compounds such as β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), 4, 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylenebis [6- (1-methylcyclohexyl) -p-cresol], 2,2'-ethylidenebis (4,6-di-) -T-butylphenol), 2,2'-butylidenebis (2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis [3- (3-t-butyl-4-hydride) Xyl-5-methylphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], 2,2′-thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl); ) Isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate Tris (4-t-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4- Tricyclic phenolic compounds such as hydroxybenzyl) benzene; tetracyclic [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] tetracyclic phenolic compounds such as methane; bis (3,5-di -T-butyl-4-hydroxybenzylphosphonate ethyl) phosphorus-containing phenol compounds such as calcium and bis (3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl) nickel;

  Examples of amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2, Polycondensate of 6,6-tetramethylpiperidineethanol, N, N ′, N ″, N ′ ″-tetrakis- (4,6-bis- (butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino) -triazin-2-yl) -4,7-diazadecane-1,10-diamine, dibutylamine 1,3,5-triazine N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine) and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [ {6- (1,1,3 3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6 , 6-tetramethyl-4-piperidyl) imino}], tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, 2,2,6 , 6-Tetramethyl-4-piperidylbenzoate, bis- (1,2,6,6-pentamethyl-4-pepyridyl) -2- (3,5-di-t-butyl-4-hydroxybenzyl) -2- n-butyl malonate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 1,1 ′-(1,2-ethanediyl) bis (3,3,5, 5-tetramethylpiperazinone (Mixed 2,2,6,6-tetramethyl-4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, (mixed 1,2,2,6,6-pentamethyl- 4-piperidyl / tridecyl) -1,2,3,4-butanetetracarboxylate, mixed [2,2,6,6-tetramethyl-4-piperidyl / β, β, β ′, β′-tetramethyl -3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6 , 6-Pentamethyl-4-piperidyl / β, β, β ′, β′-tetramethyl-3,9- [2,4,8,10-tetraoxaspiro (5,5) undecane] diethyl] -1, 2,3,4-butanetetracarbo Sylate, N, N′-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6 Chloro-1,3,5-triazine condensate, poly [6-N-morpholyl-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imide], N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine And 1,2-dibromoethane condensate, N- (2,2,6,6-tetramethyl-4-piperidyl) -2-methyl and the like.

  Examples of amino ether antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-methoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-ethoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1- Propoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-butoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-pentyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-hexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-he Tyroxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-nonyloxy-2, 2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-decanyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1-dodecyloxy-2,2,6, 6-tetramethyl-4-piperidyl) sebacate and the like.

  Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenylditridecyl) phosphite. , Cyclic neopentanetetrayl bis (nonylphenyl) phosphite, cyclic neopentanetetrayl bis (dinonylphenyl) phosphite, cyclic neopentanetetrayl tris (nonylphenyl) phosphite, cyclic neopentanetetrayl Tris (dinonylphenyl) phosphite, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diisodecylpentaerythritol diphosphite, tris Such as 2,4-di -t- butyl-phenyl) phosphite.

  The content ratio of the polymer component in the adhesive of the present invention is preferably 20% by weight to 99% by weight, more preferably 30% by weight to 95% by weight, based on the solid content of the adhesive. More preferably, it is 40 to 90% by weight, and particularly preferably 50 to 80% by weight. When the content ratio of the polymer component in the adhesive of the present invention falls within the above range, the effect that it is very difficult to peel off from the adherend even when exposed to a high-temperature atmosphere such as in a fire can be sufficiently exhibited.

  As the polymer component in the adhesive of the present invention, any appropriate polymer component can be adopted as long as it is a polymer component that can exhibit tackiness. Such a polymer component is preferably at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer. The polymer component in the adhesive of the present invention may be only one type or two or more types.

  As the rubber polymer, any appropriate rubber polymer capable of exhibiting adhesiveness can be adopted.

  As the silicone polymer, any appropriate silicone polymer that can exhibit adhesiveness can be adopted.

  As the acrylic polymer, any appropriate acrylic polymer capable of exhibiting adhesiveness can be adopted. The acrylic polymer can be preferably formed from a monomer component essentially comprising an acrylic monomer. The content of the acrylic monomer in the total monomers that can be used to form the acrylic polymer is preferably 50% to 100% by weight, more preferably 55% to 98% by weight, and even more preferably. It is 60 to 95% by weight, particularly preferably 65 to 93% by weight. Only one type of acrylic monomer may be used, or two or more types may be used.

  As an acryl-type monomer, Preferably, the (meth) acrylic-acid alkylester which has an alkyl group is mentioned. Only one (meth) acrylic acid alkyl ester having an alkyl group may be used, or two or more may be used in combination. “(Meth) acryl” means “acryl” and / or “methacryl”.

  Examples of (meth) acrylic acid alkyl ester having an alkyl group include (meth) acrylic acid alkyl ester having a linear or branched alkyl group, (meth) acrylic acid alkyl ester having a cyclic alkyl group, and the like. Is mentioned. In addition, the (meth) acrylic acid alkyl ester here means monofunctional (meth) acrylic acid alkyl ester.

  Examples of the (meth) acrylic acid alkyl ester having a linear or branched alkyl group include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Isopropyl, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, (meth ) Hexyl acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, ( (Meth) acrylic acid decyl, (meth) acrylic acid isodecyl, (meth) a Undecyl silylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate, (meth) acrylic (Meth) acrylic acid alkyl ester having 1 to 20 carbon atoms, such as octadecyl acid, nonadecyl (meth) acrylate, and eicosyl (meth) acrylate. Among these, Preferably, it is a (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in the alkyl group, and more preferably a (meth) acrylic acid alkyl ester having 2 to 10 carbon atoms in the alkyl group. .

  Examples of the (meth) acrylic acid alkyl ester having a cyclic alkyl group include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate.

  A polyfunctional monomer can be used as a monomer component that can form an acrylic polymer. Any appropriate multifunctional monomer can be adopted as the multifunctional monomer. By employing a polyfunctional monomer, a crosslinked structure can be imparted to the acrylic polymer. Only 1 type may be used for a polyfunctional monomer and it may use 2 or more types together.

  Examples of the polyfunctional monomer include 1,9-nonanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and (poly) ethylene glycol. Di (meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, allyl (meth) acrylate, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester Acrylate, urethane acrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butanediol (meth) acrylate, 2-hydroxyethyl (meta ) Acrylate, 4-hydroxybutyl (meth) acrylate, glycidyl ether 2-isocyanatoethyl acrylate, isocyanate ethyl (meth) acrylate, isocyanate (meth) acrylate, triglycidyl isocyanurate, (meth) acrylic acid, monohydroxy phthalate Ethyl (meth) acrylate, hexahydroxyphthalic acid monohydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, dimethyl (meth) acrylamide, diethyl (meth) acrylamide, isopropyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, 1,4-butanediol diglycidyl Ether, 1,2-ethanediol diglycidyl ether, polyethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, triphenyl Methane triisocyanate, methyl triisocyanate silane, tetraisocyanate silane, polyisocyanate, oxalic acid, Ronic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, 1,2,3-propanetricarboxylic acid, ethylene glycol, diethylene glycol, propylene glycol, dipropylene Glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,2,4-butanetriol, polyoxypropylenetriol, trimethylolethane, tri Methylolpropane, aminomethanol, 2-aminoethanol, 3-amino-1-propanol, diethanolamine, triethanolamine, N, N-di-n-butylethanolamine, ethylenediamine, hexamethylenediamine, tolylene Mines, hydrogenated tolylenediamine, diphenylmethanediamine, hydrogenated diphenylmethanediamine, tolidineamine, naphthalenediamine, isophoronediamine, xylenediamine, hydrogenated xylenediamine, vinylamine, 2- (2-thienyl) vinylamine, 1- (allyloxy) vinylamine , Allyl alcohol, 1,3-butadiene monoepoxide, 1-vinyl-3,4-epoxycyclohexane and the like. Among these, acrylate-based polyfunctional monomers are preferable because of high reactivity, and 1,9-nonanediol di (meth) acrylate and 1,6-hexanediol di (meth) acrylate are more preferable. 4-hydroxybutyl acrylate glycidyl ether.

  As a monomer component capable of forming an acrylic polymer, a polar group-containing monomer can be used. Any appropriate polar group-containing monomer can be adopted as the polar group-containing monomer. By adopting the polar group-containing monomer, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Only 1 type may be used for a polar group containing monomer, and it may use 2 or more types together.

  Examples of polar group-containing monomers include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, isocrotonic acid, and other carboxyl group-containing monomers or anhydrides thereof (such as maleic anhydride); (meth) acrylic Hydroxyl-containing monomers such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, vinyl alcohol, allyl alcohol, etc .; (meth) acrylamide, N, N-dimethyl Amide group-containing monomers such as (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide; aminoethyl (meth) acrylate, (meth) acrylic acid Zimechi Amino group-containing monomers such as aminoethyl and t-butylaminoethyl (meth) acrylate; Glycidyl group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; Cyano groups such as acrylonitrile and methacrylonitrile Containing monomer: N-vinyl-2-pyrrolidone, (meth) acryloylmorpholine, N-vinylpyridine, N-vinylpiperidone, N-vinylpyrimidine, N-vinylpiperazine, N-vinylpyrrole, N-vinylimidazole, N- Heterocycle-containing vinyl monomers such as vinyl oxazole; (meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; monomers containing sulfonic acid groups such as sodium vinyl sulfonate ; 2-phosphoric acid group-containing monomers such as hydroxyethyl acryloyl phosphate; and the like; isocyanate group-containing monomers such as 2-methacryloyloxyethyl isocyanate; cyclohexyl maleimide, imide group-containing monomers such as isopropyl maleimide. The polar group-containing monomer is preferably a carboxyl group-containing monomer or an anhydride thereof, and more preferably acrylic acid.

  As a monomer component capable of forming an acrylic polymer, other copolymerizable monomers can be used. Any appropriate other copolymerizable monomer can be adopted as the other copolymerizable monomer. By employing other copolymerizable monomers, it becomes possible to improve the cohesive strength of the acrylic polymer or to improve the adhesive strength of the acrylic polymer. Other copolymerizable monomers may be used alone or in combination of two or more.

  Other copolymerizable monomers include, for example, (meth) acrylic acid alkyl esters such as (meth) acrylic acid esters having an aromatic hydrocarbon group such as phenyl (meth) acrylate; vinyl such as vinyl acetate and vinyl propionate Esters; aromatic vinyl compounds such as styrene and vinyltoluene; olefins or dienes such as ethylene, butadiene, isoprene and isobutylene; vinyl ethers such as vinyl alkyl ether; vinyl chloride; methoxyethyl (meth) acrylate, (meth) (Meth) acrylic acid alkoxyalkyl monomers such as ethoxyethyl acrylate; sulfonic acid group-containing monomers such as sodium vinyl sulfonate; phosphate group-containing monomers such as 2-hydroxyethylacryloyl phosphate; cyclohexyl Maleimide, imide group-containing monomers such as isopropyl maleimide; fluorine-containing (meth) acrylate; 2-methacryloyloxy isocyanate group-containing monomers such as acryloyloxyethyl isocyanate silicon atom-containing (meth) acrylate; and the like.

  The weight average molecular weight of the acrylic polymer is preferably 300,000 or more, more preferably 400,000 to 3,000,000. The weight average molecular weight of the acrylic polymer can be determined by a gel permeation chromatography method (GPC method).

  The adhesive of the present invention may contain any appropriate other component in addition to the above-described antioxidant, as long as the effects of the present invention are not impaired, in addition to the sinterable particles and the polymer component. . Such other components may contain only 1 type, and may contain 2 or more types.

  Other components include, for example, other polymer components, softeners, anti-aging agents, curing agents, plasticizers, fillers, thermal polymerization initiators, photopolymerization initiators, ultraviolet absorbers, light stabilizers, colorants ( Pigments and dyes), solvents (organic solvents), surfactants (eg, ionic surfactants, silicone surfactants, fluorosurfactants, etc.), crosslinking agents (eg, polyisocyanate crosslinking agents, silicones) System crosslinking agents, epoxy crosslinking agents, alkyl etherified melamine crosslinking agents, etc.). In addition, a thermal polymerization initiator and a photoinitiator may be contained in the material for forming a polymer component.

  Any appropriate thermal polymerization initiator can be adopted as the thermal polymerization initiator. Examples of such thermal polymerization initiators include peroxide polymerization initiators such as hydrogen peroxide, benzoyl peroxide, and t-butyl peroxide; 2,2′-azobis-2-methylpropioaminate 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-N, N′-dimethyleneisobutylaminate, 2,2′-azobisisobutyronitrile, 2,2 And azo polymerization initiators such as' -azobis-2-methyl-N- (2-hydroxyethyl) propionamide; Only one type of thermal polymerization initiator may be used, or two or more types may be used in combination. Such a thermal polymerization initiator may be used as a redox polymerization initiator in combination with a reducing agent. Examples of such a reducing agent include ionized salts such as sulfites, hydrogen sulfites, iron, copper, and cobalt salts; amines such as triethanolamine; reducing sugars such as aldose and ketose;

  The content ratio of the thermal polymerization initiator in the adhesive of the present invention is preferably 5 parts by weight or less, more preferably with respect to the monomer component used to form the polymer component of the adhesive. It is 0.01 weight part-5 weight part, More preferably, it is 0.05 weight part-3 weight part.

  Arbitrary appropriate photoinitiators can be employ | adopted as a photoinitiator. Examples of such photopolymerization initiators include benzoin ether photopolymerization initiators, acetophenone photopolymerization initiators, α-ketol photopolymerization initiators, aromatic sulfonyl chloride photopolymerization initiators, and photoactive oxime systems. Examples include photopolymerization initiators, benzoin photopolymerization initiators, benzyl photopolymerization initiators, benzophenone photopolymerization initiators, ketal photopolymerization initiators, and thioxanthone photopolymerization initiators. Only 1 type may be used for a photoinitiator and it may use 2 or more types together.

  Examples of the ketal photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one (for example, trade name “Irgacure 651” (manufactured by Ciba Specialty Chemicals), etc.). It is done. Examples of the acetophenone photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone (for example, trade name “Irgacure 184” (manufactured by Ciba Specialty Chemicals), etc.), 2,2-diethoxyacetophenone, 2,2- Examples include dimethoxy-2-phenylacetophenone, 4-phenoxydichloroacetophenone, and 4- (t-butyl) dichloroacetophenone. Examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the acylphosphine oxide photopolymerization initiator include trade name “Lucirin TPO” (manufactured by BASF). Examples of the α-ketol photopolymerization initiator include 2-methyl-2-hydroxypropiophenone and 1- [4- (2-hydroxyethyl) phenyl] -2-methylpropan-1-one. . Examples of the aromatic sulfonyl chloride photopolymerization initiator include 2-naphthalenesulfonyl chloride. Examples of the photoactive oxime photopolymerization initiator include 1-phenyl-1,1-propanedione-2- (o-ethoxycarbonyl) -oxime. Examples of the benzoin photopolymerization initiator include benzoin. Examples of the benzyl photopolymerization initiator include benzyl. Examples of the benzophenone photopolymerization initiator include benzophenone, benzoylbenzoic acid, 3,3′-dimethyl-4-methoxybenzophenone, polyvinylbenzophenone, α-hydroxycyclohexyl phenyl ketone, and the like. Examples of the thioxanthone photopolymerization initiator include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

  The content ratio of the photopolymerization initiator in the adhesive of the present invention is preferably 5 parts by weight or less, more preferably with respect to the monomer component used to form the polymer component of the adhesive. It is 0.01 weight part-5 weight part, More preferably, it is 0.05 weight part-3 weight part.

  The adhesive of the present invention has tackiness before sintering. The adhesive of the present invention preferably has a peel rate of 50 mm / min, a peel angle of 180 °, and a 23 ° C. adhesive strength of 0.1 N / 10 mm to 15 N / 10 mm before sintering. More preferably, it is 0.5N / 10mm-10N / 10mm, More preferably, it is 1N / 10mm-8N / 10mm, Most preferably, it is 2N / 10mm-6N / 10mm. When the adhesive strength is within the above range, the adherends can be fixed instantly, the adherends can be reattached, and the sheet can be cut out in a sheet shape. Can exhibit high tackiness. A specific method for measuring the adhesive strength will be described later.

  The adhesive of the present invention has sinterability. Arbitrary appropriate temperature can be employ | adopted for sintering temperature according to the kind and quantity of sinterable particle | grains contained in the adhesive agent of this invention.

  Arbitrary appropriate forms can be employ | adopted for the adhesive agent of this invention. As a form of the adhesive agent of this invention, a sheet form and a tape form are mentioned, for example. When the form of the adhesive of the present invention is a sheet, it can be used as an adhesive sheet. The adhesive of the present invention may have a form in which a sheet or tape is wound into a roll. The adhesive of the present invention may have a form in which sheets or tapes are laminated.

  When the adhesive of the present invention is a sheet, the thickness is preferably 1 μm to 1000 μm, more preferably 5 μm to 500 μm, still more preferably 10 μm to 300 μm, and particularly preferably 20 μm to 200 μm. is there. When the thickness of the adhesive of the present invention is within the above range, the handleability as an adhesive sheet is excellent.

  The adhesive of the present invention can be manufactured by any appropriate method as long as it is a manufacturing method capable of obtaining an adhesive including sinterable particles and a polymer component.

  As a preferred method for producing the adhesive of the present invention, for example, a polymerizable syrup is obtained by partially polymerizing a polymerizable composition containing a monomer component used to form a polymer component and any appropriate photopolymerization initiator. Is prepared, and sinterable particles are added to the polymerizable syrup and uniformly dispersed, and then coated on any appropriate base material (separator, etc.) and irradiated with light to be photopolymerized (cured). A method is mentioned.

  Arbitrary appropriate conditions can be employ | adopted about conditions, such as a light source in the case of light irradiation, irradiation energy, an irradiation method, and irradiation time.

  Examples of active energy rays used for light irradiation include ionizing radiation such as α rays, β rays, γ rays, neutron rays, and electron rays, and ultraviolet rays. Preferably it is an ultraviolet-ray.

  Examples of irradiation with active energy rays include irradiation with a black light lamp, a chemical lamp, a high-pressure mercury lamp, a metal halide lamp, and the like.

  Heating may be performed during the polymerization. Any appropriate heating method can be adopted as the heating method. Examples of the heating method include a heating method using an electric heater, a heating method using electromagnetic waves such as infrared rays, and the like.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  The separators and cover separators used in each of the following examples are both 38 μm thick biaxially stretched polyethylene terephthalate film (trade name “MRN38”, Mitsubishi Chemical Polyester Film Co. Company).

[Synthesis Example 1] (Preparation of photopolymerizable syrup (A))
As monomer components, 2-ethylhexyl acrylate: 90 parts by weight, acrylic acid: 10 parts by weight, photopolymerization initiator (trade name “Irgacure 651”, manufactured by BASF): 0.05 part by weight, and photopolymerization initiator (trade name) "Irgacure 184" (manufactured by BASF): Nitrogen gas after stirring 0.05 parts by weight in a four-necked separable flask equipped with a stirrer, thermometer, nitrogen gas inlet tube and cooling tube until uniform Was carried out for 1 hour to remove dissolved oxygen. Thereafter, the composition was polymerized by irradiating ultraviolet rays from the outside of the flask with a black light lamp. When the viscosity reached an appropriate level, the lamp was turned off, and the nitrogen blowing was stopped, and a partially polymerized composition having a polymerization rate of 7%. A photopolymerizable syrup (A) was prepared.

[Example 1]
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE): 10 Part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2, yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A cover separator was used, and a black light lamp was used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) were irradiated and cured for 5 minutes to produce a sheet-like adhesive (1) having a thickness of 100 μm.
The obtained adhesive (1) was evaluated. The results are shown in Table 1.

[Example 2]
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE): 50 Part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2, yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A cover separator was used, and a black light lamp was used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) were irradiated and cured for 5 minutes to produce a sheet-like adhesive (2) having a thickness of 100 μm.
The obtained adhesive (2) was evaluated. The results are shown in Table 1.

Example 3
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, urethane acrylate (manufactured by Daicel Cytec Co., Ltd., EBECRYL 9260) : 3 parts by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2, yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and uniformly dispersed with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A cover separator was used, and a black light lamp was used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) were irradiated and cured for 5 minutes to produce a sheet-like adhesive (3) having a thickness of 100 μm.
The obtained adhesive (3) was evaluated. The results are shown in Table 1.

Example 4
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, 4-hydroxybutyl acrylate glycidyl ether (4HBAGE): 10 Part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2, yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A glass cloth (manufactured by Unitika, E10T-4W, thickness: 100 μm) is placed on the coated surface obtained, a cover separator is used, a black light lamp is used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) are applied. It was cured by irradiating for minutes to produce an adhesive (4) with a sheet-like substrate having a thickness of 200 μm (adhesive layer: 100 μm, glass cloth: 100 μm).
The obtained adhesive (4) was evaluated. The results are shown in Table 1.

[Comparative Example 1]
Photopolymerizable syrup obtained in Synthesis Example 1 (A): 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2 , Yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A cover separator was used, and a black light lamp was used as a light source, which was cured by irradiation with ultraviolet rays (illuminance: 5 mW / cm ² ) for 5 minutes to produce a sheet-like adhesive (C1) having a thickness of 100 μm.
The obtained adhesive (C1) was evaluated. The results are shown in Table 1.

[Comparative Example 2]
Photopolymerizable syrup (A) obtained in Synthesis Example 1: 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, urethane acrylate (manufactured by Daicel Cytec Co., Ltd., EBECRYL 9260) 1 part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2, yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A cover separator was used, and a black light lamp was used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) were irradiated and cured for 5 minutes to produce a sheet-like adhesive (C2) having a thickness of 100 μm.
The obtained adhesive (C2) was evaluated. The results are shown in Table 1.

[Comparative Example 3]
Photopolymerizable syrup obtained in Synthesis Example 1 (A): 100 parts by weight, 1,6-hexanediol diacrylate (HDDA): 0.1 part by weight, glass powder (manufactured by Takara Standard Co., Ltd., VY-0114M2 , Yield point: 397 ° C., average particle size: 10 μm): 50 parts by weight were added and dispersed uniformly with a disper. The obtained dispersion was coated on the separation-treated surface of the separator so as to have a thickness of 100 μm. A glass cloth (manufactured by Unitika, E10T-4W, thickness: 100 μm) is placed on the coated surface obtained, a cover separator is used, a black light lamp is used as a light source, and ultraviolet rays (illuminance: 5 mW / cm ² ) are applied. It was cured by irradiation for minutes to produce a sheet-like substrate-attached adhesive (C3) having a thickness of 200 μm (adhesive layer: 100 μm, glass cloth: 100 μm).
The obtained adhesive (C3) was evaluated. The results are shown in Table 1.

<Evaluation of adhesiveness>
A 25 mm wide sample was pressed against a standard glass plate using a 2 kg rubber roller at a speed of 300 mm / min while the roller was rolled back and forth once. Twenty-four hours after pressure bonding, the film was pulled in the 180 ° direction at 23 ° C. and at a tensile speed (peeling speed) of 300 mm / min, and the adhesive strength was evaluated.

<Evaluation of high-temperature tackiness and high-temperature adhesiveness>
(High temperature tack test * 1)
The adhesives obtained in Examples and Comparative Examples were cut out to 30 mm × 50 mm and bonded to a 30 mm × 30 mm glass plate to prepare a test body in which the adhesive was protruded 20 mm from the glass plate. The test body was attached to a stainless steel jig as shown in FIG. 2, and further fixed between stainless steel plates using fixing screws.
The test body fixed to the jig was placed in an electric furnace maintained at 200 ° C., and allowed to stand in a high temperature atmosphere for 10 minutes under the condition of a temperature increase rate of 15 ° C./min. Thereafter, the test body is taken out, the adhesion state of the test body and the glass plate is visually observed, ○ when the test body and the glass plate are not peeled, Δ when the peeling of the test body and the glass plate is less than half, The case where the test body and the glass plate were peeled off by half or more was evaluated as x.
(High temperature adhesion test * 2)
Using the adhesives obtained in Examples and Comparative Examples, a test specimen was prepared and fixed to a jig in the same manner as the high-temperature tack test * 1. Then, it put into the electric furnace hold | maintained at 700 degreeC, and left still in a high temperature atmosphere for 10 minutes on the conditions of the temperature increase rate of 20 degrees C / min. Then, the test specimen is taken out, the adhesion state of the test specimen and the glass plate is visually observed, and the case where the test specimen and the glass plate are not peeled is evaluated as ◯, and the case where the test specimen and the glass plate are peeled is evaluated as x. did.

  The adhesive of the present invention has little peeling from the glass plate even when exposed to a high temperature of 200 ° C, and does not peel from the glass plate even when exposed to a high temperature of 700 ° C. Was confirmed. On the other hand, the adhesive shown in the comparative example peels more than half from the glass plate when exposed to a high temperature of 200 ° C, and completely peels from the glass plate when exposed to a high temperature of 700 ° C. It was confirmed.

  Therefore, the adhesive of the present invention can fix the adherends instantly, can reattach the adherends, is excellent in workability such as being cut out in a sheet shape, Even when exposed to a high-temperature atmosphere such as a fire, it does not peel off from the adherend, indicating that it has excellent heat resistance.

  The adhesive of the present invention can instantly fix the adherends to each other, can reattach the adherends, and further from the adherend when exposed to a high-temperature atmosphere such as a fire. Does not peel off and has excellent heat resistance. Therefore, the adhesive of the present invention can be effectively used not only for applications that are not exposed to a high temperature atmosphere but also for applications that are exposed to a high temperature atmosphere.

10 Polymer Component 20 Sinterable Particle 100 Adhesive 200 Glass Plate 300 Specimen 400 Fixing Screw

Claims (10)

It is an adhesive having adhesiveness before sintering and having adhesiveness after sintering,
Including sinterable particles and a polymer component;
The polymer component has a crosslinked structure;
Adhesive.   The pressure-sensitive adhesive according to claim 1, comprising a crosslinkable monomer in a content ratio of 2.0 wt% to 60 wt% in all monomer components constituting the polymer component.   The adhesive according to claim 2, wherein the crosslinkable monomer has at least one functional group selected from an acryloyl group, an epoxy group, an isocyanate group, a carboxyl group, a hydroxyl group, a vinyl group, and an amino group.   The adhesive according to any one of claims 1 to 3, wherein a yield point of the sinterable particles is 250 ° C to 800 ° C.   The sinterable particles are formed of at least one component selected from silicic acid, boric acid, borosilicate, aluminum oxide, calcium oxide, sodium oxide, lithium oxide, and phosphorus oxide. The adhesive agent in any one.   The adhesive agent in any one of Claim 1-5 whose average particle diameter of the said sinterability particle | grain is 0.1 micrometer-1000 micrometers.   The adhesive agent in any one of Claim 1-6 whose content rate of the said sinterable particle | grain is 1 weight%-80 weight% with respect to solid content of the said adhesive agent.   The adhesive according to any one of claims 1 to 7, wherein the polymer component is at least one component selected from a rubber-based polymer, a silicone-based polymer, and an acrylic polymer.   The adhesive agent in any one of Claim 1-8 which is a sheet form.   The adhesive agent of Claim 9 whose thickness is 1 micrometer-1000 micrometers.