JPWO2016111358A1 - Composite heating material and manufacturing method thereof - Google Patents

Abstract

The heating element and the heat-dissipating rubber insulator are molecularly bonded by chemical bonding without interposing an air layer or adhesive layer, and without causing an air layer due to heat shock or thermal expansion difference or peeling at the interface between them. Highly heat-conducting efficiency from the heating element to the heat-dissipating rubber insulator, excellent heat dissipation, tackiness, adhesiveness, bending fatigue resistance, flexibility, UV durability, heat resistance and waterproofing, heating Provided is a composite heat generating material that can be efficiently heated by high adhesion to an object. In the composite heat generating material (1), the heat dissipating rubber insulator (5) and at least a part of the heat generating body (4) are directly at the active groups on the surface of each other and / or indirectly through a molecular adhesive. They are joined and integrated by simple covalent bonds.

Description

  The present invention relates to a composite heating material in which a heating element and a heat-dissipating rubber insulator are integrated, and a method for manufacturing the same.

  Conventionally, as a heat generating material for heating an object to be heated for melting snow, preventing freezing, and for heating, an energizing member that conducts electricity such as an electrode and wiring and a heat generating member that generates heat such as a resistor are high. A structure having a heat generating member while joining a current-carrying member and a soaking plate such as a metal plate has been used which is covered with an electrical insulating sheet such as a molecular resin film.

  For example, in Patent Document 1, an electrode that is electrically connected to a PTC resistor calendar product in which a mesh-like polyester non-woven fabric and a thin-film PTC (Positive Temperature Coefficient) resistor are bonded together by calendering. A planar heating element having an upper surface and a lower surface covered with a polyester film via a hot melt adhesive is disclosed. This planar heating element is thin and environmentally friendly, and can be suitably used for heating for an electric vehicle (EV) or for heating a lithium ion battery.

  Generally, a heating element covered with a polymer resin film is not suitable for outdoor use in building materials for the purpose of melting snow because it easily deteriorates due to ultraviolet rays. In addition, since the resistor and the film are bonded via an adhesive, the adhesive and its adhesive layer are likely to deteriorate due to long-term use, and there is a problem that peeling occurs at the interface between them. Even if it has flexibility, it is likely to be peeled off while being bent and used for a long time or repeatedly bent and stretched.

  As an example in which such an adhesive is not used, for example, in Patent Document 2, a heat generating element composed of a metal foil resistor or a metal resistor and a polyarylene sulfide film serving as an insulating film are thermocompression bonded under high temperature and pressure. Thus, a sheet heating element in which they are bonded without using an adhesive is disclosed. According to thermocompression bonding, peeling of the interface due to deterioration of the adhesive can be somewhat improved at high temperatures and high humidity. While bending and stretching are repeated, peeling occurs from this, and heat conduction efficiency decreases. Further, since the insulating coating is a resin film, it cannot follow a heat shock or a thermal expansion difference due to a temperature change, and there is a problem that an air layer is generated at the interface and a decrease in heat conduction efficiency is increased.

  Patent Document 3 discloses a composite heating material in which a heating element and a soaking plate such as a metal plate are not directly joined and an air layer is not interposed therebetween. This composite heating material is integrated by inserting a heating element between the soaking plate and the soaking plate, or between the soaking plate and the heat insulating material, pressing between them and fixing with pressure, Instead of being fixed with an adhesive or a screw, the heating element and the soaking plate are integrated with each other via a material that absorbs the expansion / contraction difference. Such a heat generating material is less likely to be peeled off at the interface as compared with the case where an air layer is interposed between the heating element and the heat equalizing plate, and can improve thermal conductivity, but the heat equalizing plate is a rigid metal plate. Due to the lack of flexibility, there is a problem that the adhesion with a non-planar heating object is poor, and the thermal conductivity of the corner cannot be fully utilized, resulting in low heat conduction efficiency.

JP 2012-227034 A JP 2009-123463 A JP 2001-85145 A

  The present invention has been made in order to solve the above-mentioned problems, and the heating element and the heat-dissipating rubber insulator are molecularly bonded by chemical bonding without interposing an air layer or an adhesive layer, thereby causing a heat shock or thermal expansion difference. Strongly bonded without creating an air layer or peeling at the interface between them, heat conduction efficiency from the heating element to the heat dissipation rubber insulator is high, heat dissipation, tackiness, adhesiveness, bending fatigue resistance, An object of the present invention is to provide a composite heating material that is excellent in flexibility, ultraviolet durability, heat resistance, water resistance, and waterproofness, and that can be efficiently heated with high adhesion to a heating object, and a method for producing the same.

  In order to achieve the above object, the composite heat generating material of the present invention comprises a heat-dissipating rubber insulator and at least a part of the heat generating member directly and / or molecular adhesives with active groups on each other surface. It is characterized by being joined and integrated by an indirect covalent bond via the.

  In the composite heat generating material, at least one of a dry treatment selected from a corona treatment, a plasma treatment, and an ultraviolet irradiation treatment and a molecular adhesive treatment on the surface of at least one of the heat-radiating rubber insulator and the heat-generating body. May be joined and integrated by the covalent bond.

  In the composite heating material, the heating element covers a resistance in the form of a thread, a wire, a film, a plate, a coil, a mesh, a mesh, a foil, a fabric, a film or a layer, or the resistance. It is selected from a flexible heater, a flexible film heater, and a flexible rubber heater having a covering resistance having a woven fabric, a nonwoven fabric, a film material or a rubber material, and a wiring connected to the resistance. At least one of the heaters is preferable.

  In the composite heating material, the resistance may be formed of at least one of nickel chrome, iron chrome, copper nickel, copper manganese, conductive resistance ink, and conductive resistance fiber.

  In the composite heating material, the heating element is preferably planar.

  The composite heating material may be one in which the heating element is coated with a polymer resin.

  In the composite heat generating material, the heat radiation rubber insulator is formed of at least one rubber material selected from silicone rubber, ethylene-propylene-diene-methylene copolymer rubber, urethane rubber, and fluorine rubber. preferable.

  The composite heat generating material may have a multilayer structure in which the heat radiating rubber insulator is formed of the rubber material.

  In the composite heat generating material, the heat radiating rubber insulator may be covered with a film formed of a resin material or a rubber material.

  In the composite heat generating material, the heat-dissipating rubber insulator is bonded to one surface of the heat generating member by the covalent bond, and the heat insulating material is directly and / or molecularly bonded to the active surface of the other surface. They may be integrated by indirect covalent bonding via an agent.

  The method of manufacturing the composite heating material includes a heating element and a rubber material or a heat dissipation rubber insulator that becomes a heat dissipation rubber insulator, directly and / or indirectly via a molecular adhesive, under normal pressure, under pressure or Contacting under reduced pressure to form a covalent bond directly and / or indirectly through the molecular adhesive with the active groups of each other, and at least a portion of the heating element and the heat dissipating rubber insulator Are bonded and integrated by the covalent bond.

  The composite heating material of the present invention is molecularly bonded by a chemical bond without interposing an air layer or an adhesive layer at the interface between the heating element and the heat-dissipating rubber insulator. They are firmly joined without any gap or separation at their interface. Therefore, the heat conduction efficiency from the heating element to the heat radiating rubber insulator is high, and the object to be heated can be efficiently heated. Moreover, the composite heat generating material can improve a heating effect by the outstanding adhesiveness to a heating target object and high heat dissipation. Furthermore, this composite heating material has tackiness, adhesiveness, bending fatigue resistance, flexibility, UV durability, heat resistance and waterproofness, and can be used not only indoors but also outdoors, Even in an environment such as a high humidity, it can be used stably for a long period of time without causing warpage due to deterioration, peeling or thermal expansion difference.

  According to the method for manufacturing a composite heating material of the present invention, the heating element and the heat-dissipating rubber insulator can be firmly bonded by molecular adhesion without using an adhesive, which contributes to a reduction in production cost.

It is a schematic cross section of a composite heating material to which the present invention is applied. It is a schematic cross section of another composite heating material to which the present invention is applied. It is a schematic cross section of another composite heating material to which the present invention is applied. It is a figure which shows the correlation with the elapsed time and temperature in the thermal conductivity test using the composite heat generating material of Example 1 to which this invention is applied, and the composite heat generating material of Comparative Examples 1 and 2 to which this invention is not applied.

  Hereinafter, although the preferable form for implementing this invention is demonstrated in detail, the scope of the present invention is not limited to these forms.

  In the composite heating material of the present invention, the heating element and the heat-dissipating rubber insulator are bonded by peeling the active groups on the surfaces of each other by direct covalent bonding or molecular bonding by indirect covalent bonding through a molecular adhesive. It is impossible to integrate.

  One embodiment of this composite heating material will be described in detail with reference to FIG.

  The composite heating material 1 includes a heating element 4 having a heating member 2 that is a resistance formed of a woven fabric or a nonwoven fabric containing conductive fibers, and a current-carrying member 3 that is a pair of electrodes that serve as a wiring for energizing the heating member. It is sealed with the heat dissipating rubber insulator 5. The contact surface where the heating element 4 and the heat-dissipating rubber insulator 5 are in contact with each other is firmly bonded by the chemical bonding of the active groups on the respective surfaces and molecular adhesion. Therefore, the upper surface of the heating element 4 and the heat radiation rubber insulator layer 5a covering the upper surface are respectively on the contact surface between the heat generation member 2 and the heat radiation rubber insulator 5 and the contact surface between the current-carrying member 3 and the heat radiation rubber insulator 5. These are molecules that are bonded by chemical bonding and bonded together. Similarly, the lower surface of the heating element 4 and the heat-dissipating rubber insulator layer 5b covering the heat-generating element 4 are molecularly bonded and bonded to each other at the contact surface between the energizing member 3 and the heat-dissipating rubber insulator 5 by chemical bonding. It is what. Further, the composite heat generating material 1 is configured such that the heat dissipating rubber insulator layer 5a and the heat dissipating rubber insulator are sandwiched between the heat dissipating rubber insulator layer 5a and the heat dissipating rubber insulator layer 5b, which are larger than the heat generating member 4. The layer 5b is in contact, and the heat radiation rubber insulator 5 is formed on the contact surface by chemically bonding the active groups on the surfaces of the layers 5 and molecularly bonding them.

  The heating element 4 is a fiber structure in which a band-shaped energizing member 3 composed of a pair of electrodes is laminated and adhered to both ends of a heating member 2 formed in a rectangular sheet shape including conductive fibers. .

  The heat generating member 2 is a woven fabric or a non-woven fabric including fibers having electrical conductivity and electrical resistance, and may include a synthetic fiber or a non-synthetic fiber. Examples of synthetic fibers include polyester resins, polyamide resins, acrylic resins, polyvinyl alcohol resins, polyolefin resins, and polyurethane resins. Examples of non-synthetic fibers include natural fibers such as cotton, hemp, wool, and silk; regenerated fibers such as rayon and cupra; and semi-synthetic fibers such as acetate fibers. Any shape, thickness, and size of the heat generating member 2 can be appropriately selected.

  The energizing member 3 is electrically conductive and is not particularly limited as long as it is connected to the heat generating member 2 and can be energized, and may be an electrode or heating wire formed of a metal material, a carbon material, or a ceramic material. Yes, any shape, thickness, size, etc. can be selected as appropriate.

  The fiber structure as the heating element 4 may be a structure in which a linear or bar-shaped heating wire such as a nichrome wire or carbon fiber that generates heat when energized is attached to or included in a cloth or cloth.

  The heat dissipating rubber insulator 5 includes at least a rubber material, and is formed of a rubber composition including a heat conductive filler and an additive as required. The heat-dissipating rubber insulator 5 forms a chemical bond to form a molecule even if the surface of the heating element 4 to be joined has a smooth surface such as a metal or an uneven surface such as a fiber. It can be bonded and can be bonded and bonded without gaps.

  The rubber hardness of the heat dissipating rubber insulator 5 is 5 to 80 in Shore A hardness. When the hardness is too low, the thermal conductivity is low, and when the hardness is too high, the flexibility is inferior, so this range is preferable. More preferably, the Shore A hardness is 10 to 60. The thickness of the heat dissipating rubber insulator 5 is 0.01 mm to 10 mm. If it is too thin, it is difficult to process, and if it is too thick, the thermal conductivity becomes low, so this range is preferable. More preferably, it is 0.05 mm-2 mm.

  Specific examples of the rubber material for the heat dissipating rubber insulator 5 include silicone rubber, ethylene-propylene-diene-methylene copolymer rubber (EPDM), urethane rubber, and fluorine rubber. These rubber materials may be composed of one kind or a plurality of kinds. The heat-dissipating rubber insulator 5 is made of at least a heat-dissipating rubber material, and further performance and functions can be imparted depending on the rubber material used. Of these rubber materials, silicone rubber is preferable from the viewpoint of improving flexibility, tackiness, and followability, and EPDM is preferable from the viewpoint of reducing gas permeability and improving waterproofness.

  The silicone rubber used as the rubber material of the heat dissipating rubber insulator 5 is mainly composed of peroxide-crosslinked silicone rubber, addition-crosslinked silicone rubber, condensation-crosslinked silicone rubber, or a co-blend of these silicone rubber and non-silicone rubber. . By using the heat-dissipating rubber insulator 5 formed of silicone rubber, it exhibits high flexibility in a wide temperature range such as −40 ° C. to 200 ° C., and can improve bending fatigue resistance and followability. Expansion due to heat shock can be prevented. These silicone rubbers have a number average molecular weight of 10,000 to 1,000,000.

  The peroxide-crosslinked silicone rubber that is the material of the heat-dissipating rubber insulator 5 is not particularly limited as long as it is synthesized using a silicone raw material compound that can be crosslinked with a peroxide-based crosslinking agent. , Vinyl methylsiloxane / polydimethylsiloxane copolymer, vinyl terminated polydimethylsiloxane, vinyl terminated diphenylsiloxane / polydimethylsiloxane copolymer, vinyl terminated diethylsiloxane / polydimethylsiloxane copolymer, vinyl terminated trifluoropropylmethylsiloxane / polydimethylsiloxane copolymer, vinyl Terminal polyphenylmethylsiloxane, vinylmethylsiloxane / dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane Polymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / diphenylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / ditrifluoropropylmethylsiloxane copolymer, trimethylsiloxane-terminated polyvinylmethylsiloxane, methacryloxypropyl-terminated poly Examples include dimethylsiloxane, acryloxypropyl group-terminated polydimethylsiloxane, (methacryloxypropyl) methylsiloxane / dimethylsiloxane copolymer, and (acryloxypropyl) methylsiloxane / dimethylsiloxane copolymer.

  Examples of the peroxide-based crosslinking agent to be coexisted include ketone peroxides, diacyl peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and percarbonates. Include ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, peroxycarbonate, peroxy ester, benzoyl peroxide, dicumyl peroxide, dibenzoyl peroxide, t-butyl hydroperoxide, di-t-butyl Hydroperoxide, di (dicyclobenzoyl) peroxide, 2,5-dimethyl-2,5bis (t-butylperoxy) hexane, 2,5-dimethyl-2,5bis (t-butylperoxy) Xing, benzophenone, Mihiraaketon, dimethylaminobenzoic acid ethyl ester, benzoin ethyl ether.

  The amount of peroxide-based crosslinking agent used depends on the type of silicone rubber obtained, the nature of the heat-dissipating rubber insulator 5 formed from the silicone rubber, and the nature of the silane coupling agent used as necessary. Although appropriately selected, 0.01 to 10 parts by mass, preferably 0.1 to 2 parts by mass is used with respect to 100 parts by mass of the silicone rubber. If it is less than this range, the crosslinking degree is too low to be used as silicone rubber. On the other hand, when it exceeds this range, the degree of cross-linking is too high and the elasticity of the silicone rubber is reduced.

The addition-crosslinking type silicone rubber as the material of the heat-dissipating rubber insulator 5 includes vinylmethylsiloxane / polydimethylsiloxane copolymer, vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane / polydimethylsiloxane copolymer, vinyl-terminated diethyl synthesized in the presence of Pt catalyst. Siloxane / polydimethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane / polydimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylmethylsiloxane / dimethylsiloxane copolymer, trimethylsiloxane-terminated dimethylsiloxane / vinylmethylsiloxane / diphenylsiloxane copolymer, Trimethylsiloxane group-terminated dimethylsiloxane / vinylmethylsiloxane / ditrifluoropropyl Polysiloxane copolymers, vinyl group-containing polysiloxanes such as trimethylsiloxane-terminated polyvinylmethylsiloxane, H-terminated polysiloxanes, methyl-H siloxane / dimethylsiloxane copolymers, polymethyl-H siloxane, polyethyl-H siloxane, H-terminated polyphenyl (dimethyl-H siloxy) H group-containing polysiloxane composition exemplified by siloxane, methyl H siloxane / phenylmethyl siloxane copolymer, methyl H siloxane / octylmethyl siloxane copolymer, or aminopropyl terminated polydimethylsiloxane, aminopropylmethylsiloxane / dimethylsiloxane copolymer, amino Ethylaminoisobutylmethylsiloxane / dimethylsiloxane copolymer, aminoethylaminopropylmethoxysiloxa / Dimethylsiloxane copolymer, amino group-containing polysiloxane exemplified by dimethylamino-terminated polydimethylsiloxane, epoxypropyl-terminated polydimethylsiloxane, epoxy group-containing polysiloxane exemplified by (epoxycyclohexylethyl) methylsiloxane / dimethylsiloxane copolymer, It is obtained from a composition of an acid anhydride group-containing polysiloxane exemplified by succinic anhydride-terminated polydimethylsiloxane and an isocyanate group-containing compound such as toluyl diisocyanate and 1,6-hexamethylene diisocyanate. is there.

  The processing conditions for producing the heat-dissipating rubber insulator 5 from these addition-crosslinking type silicone rubber compositions vary depending on the type and characteristics of the addition reaction, and therefore cannot be uniquely determined, but generally at 0 to 200 ° C. for 1 minute. Heating for ~ 24 hours. Thereby, an addition-crosslinking type silicone rubber is obtained as the heat dissipating rubber insulator 5. When the physical properties of the silicone rubber are better under low temperature processing conditions, the reaction time becomes longer. When productivity faster than physical properties is required, the processing is performed at a high temperature for a short time. When machining must be performed within a certain period of time depending on the production process and work environment, the machining temperature is set to a relatively high temperature within the above range in accordance with the desired machining time.

Condensation-crosslinked silicone rubber as the material of the heat-dissipating rubber insulator 5 is a silanol-terminated polydimethylsiloxane, silanol-terminated polydiphenylsiloxane, silanol-terminated polytrifluoromethylsiloxane, silanol-terminated diphenylsiloxane / A composition of a single condensation component comprising a silanol-terminated polysiloxane exemplified by a dimethylsiloxane copolymer;
These silanol-terminated polysiloxanes, tetraacetoxysilane, triacetoxymethylsilane, di-t-butoxydiacetoxysilane, vinyltriacetoxysilane, tetraethoxysilane, trienoxymethylsilane, bis (triethoxysilyl) ethane, tetra -N-propoxysilane, vinyltrimethoxysilane, methyltris (methylethylketoxime) silane, vinyltris (methylethylketoxyimino) silane, vinyltriisopropenooxysilane, triacetoxymethylsilane, tri (ethylmethyl) oximemethylsilane, bis ( N-methylbenzoamido) ethoxymethylsilane, tris (cyclohexylamino) methylsilane, triacetamidomethylsilane, tridimethylaminomethylsilane Or a composition of these silanol-terminated polysiloxanes and chloro-terminated polydimethylsiloxanes, diacetoxymethyl-terminated polydimethylsiloxanes, and end-blocked polysiloxanes exemplified by terminal polysiloxanes. .

  The processing conditions for producing the heat-dissipating rubber insulator 5 from these condensation-crosslinking type silicone rubber compositions vary depending on the type and characteristics of the condensation reaction, and therefore cannot be uniquely determined, but generally at 0 to 100 ° C. for 10 minutes. Heating for ~ 24 hours. Thereby, a condensation-crosslinking type silicone rubber is obtained as the heat dissipating rubber insulator 5. When the physical properties of the silicone rubber are better under low temperature processing conditions, the reaction time becomes longer. When productivity faster than physical properties is required, the processing is performed at a high temperature for a short time. When machining must be performed within a certain period of time depending on the production process and work environment, the machining temperature is set to a relatively high temperature within the above range in accordance with the desired machining time.

  The co-blend of silicone rubber and non-silicone rubber as the material of the heat radiation rubber insulator 5 may be a co-blend of silicone rubber and olefin rubber. Non-silicone rubber used in this co-blend is ethylene-propylene-diene rubber, natural rubber, 1,4-cisbutadiene rubber, isoprene rubber, polychloroprene, styrene-butadiene copolymer rubber, hydrogenated styrene-butadiene copolymer rubber. , Acrylonitrile / butadiene copolymer rubber, hydrogenated acrylonitrile / butadiene copolymer rubber, polybutene rubber, polyisobutylene rubber, ethylene / propylene rubber, ethylene oxide-epichlorohydrin copolymer rubber, chlorinated polyethylene rubber, chlorosulfone Polyethylene rubber, alkylated chlorosulfonated polyethylene rubber, chloroprene rubber, chlorinated acrylic rubber, brominated acrylic rubber, fluoro rubber, epichlorohydrin and its copolymer rubber, chlorinated ethylene propylene , Chlorinated butyl rubber, brominated butyl rubber, homopolymer rubbers such as tetrafluoroethylene, hexafluoropropylene, vinylidene fluoride and tetrafluoroethylene and their binary and terpolymer rubbers, ethylene / tetrafluoroethylene copolymer What crosslinked the raw material rubber-like substance compound illustrated by linear polymers, such as rubber, propylene / tetrafluoroethylene copolymer rubber, ethylene acrylic rubber, epoxy rubber, urethane rubber, a both-ends unsaturated group elastomer, etc. Can be mentioned. These may be used alone or in combination.

  The heat-dissipating rubber insulator 5 has a heat conductivity selected from aluminum oxide, magnesium oxide, zinc oxide, graphite carbon, silicon nitride, boron nitride, and aluminum nitride as necessary from the viewpoint of improving thermal conductivity. It is preferable that a conductive filler powder is contained. The heat conductive filler powder preferably has an average particle size of 0.2 to 50 μm. Moreover, as content of a heat conductive filler powder, it is preferable in it being 50 to 95 weight%.

  The heat-dissipating rubber insulator 5 is made of a platinum catalyst such as a 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) catalyst (so that the active groups on the surfaces can be easily covalently bonded. Pt (dvs)) It is preferable to contain a platinum complex such as 2.1-2.4% xylene solution (product of Gelest) at a concentration of 10 to 1000 ppm in terms of platinum.

  The heat-dissipating rubber insulator 5 includes a silane coupling agent having 2 to 6 units of vinylalkoxysilane units having a vinylalkoxysilyl group, such as polyvinylmethoxysiloxane, so that the active groups on the surfaces of each other can be covalently bonded. , Preferably in a concentration of 0.5 to 10 parts by weight. The vinyl group of the silane coupling agent and the vinyl group or hydrogensiloxane group in the silicone rubber polymer can be more strongly bonded by a covalent bond different from the ether bond covalently bonded by a peroxide or a platinum catalyst. At this time, it is preferable that a platinum catalyst is contained because it becomes easier to covalently bond.

  The composite heat generating material 1 has a reactive activity such as an active group, such as a hydroxyl group (—OH) or a hydroxysilyl group (—SiOH), on the surfaces of the bonding surfaces of the heating element 4 and the heat radiation rubber insulator 5. The groups are firmly bonded by chemical bonding and molecular adhesion directly by covalent bonds. Such a chemical bond is preferably an ether bond by dehydration of OH groups. The joint surface between the heat generating member 4 and the heat radiating rubber insulator 5 is a joint surface between the heat generating member 2 and the heat radiating rubber insulator 5, and is a joint surface between the energizing member 3 and the heat radiating rubber insulator 5.

  The heating element 4 and the heat-dissipating rubber insulator 5 may be subjected to a dry process such as a corona process, a plasma process, or an ultraviolet irradiation process on a part or all of at least one surface serving as a bonding surface. The ultraviolet irradiation treatment is not limited as long as it is a treatment for irradiating ultraviolet rays, but may be a general ultraviolet ray treatment (UV treatment) for irradiating ultraviolet rays in a wide wavelength region or a plurality of wavelengths, and is regarded as a single wavelength. Excimer ultraviolet treatment (excimer UV treatment) for irradiating excimer ultraviolet rays to be applied may be used. By these dry treatments, an active group can be generated in addition to an active group such as a hydroxyl group that the surface originally has, and the active group that is originally possessed and the activated active group are opposed to each other. The heat generating body 4 and the heat dissipating rubber insulator 5 can be directly and chemically bonded to each other by forming a covalent bond with each other on the surface, specifically dehydrating to form an ether bond which is a strong covalent bond.

  The heating element 4 and the heat-dissipating rubber insulator 5 may be joined and integrated by a covalent bond via a molecular adhesive.

  A molecular adhesive is a covalent bond between a heating element and a heat-dissipating rubber insulator by a single or multimolecular molecular adhesive molecule by the chemical reaction of the functional group in the molecule with the adherend through covalent bonding. It connects directly via. A molecular adhesive is a generic term for such bifunctional molecules, in which two functional groups chemically react with a heating element and a heat-dissipating rubber insulator, respectively, which are adherends, to form a covalent bond. Specific examples include various coupling agents including a silane coupling agent.

（式(Ｉ)中、Ｗは、スペーサ基、例えば置換基を有していてもよいアルキレン基、アミノアルキレン基であってもよく、直接結合であってもよい。Ｙは、ＯＨ基又は加水分解や脱離によりＯＨ基を生成する反応性官能基、例えばトリアルコキシアルキル基である。−Ｚは、−Ｎ_３又は−ＮＲ^１Ｒ^２である。但し、Ｒ^１，Ｒ^２は同一又は異なりＨ又はアルキル基、−Ｒ^３Ｓｉ（Ｒ^４）_ｍ（ＯＲ^５）_３−ｍ[Ｒ^３，Ｒ^４はアルキル基、Ｒ^５はＨ又はアルキル基、ｍは０〜２]。なお、アルキレン基、アルコキシ、アルキル基は、置換基を有していてもよい炭素数１〜１２の直鎖状、分岐鎖状及び／又は環状の炭化水素基である。）で表わされるトリアジン化合物；
トリアルコキシシリルアルキル基を有するチオール化合物；
トリアルキルオキシシリルアルキル基を有するエポキシ化合物；
CH₂=CH-Si(OCH₃)₂-O-[Si(OCH₃)₂-O-]_n-Si(OCH₃)₂-CH=CH₂ (n=1.8〜5.7)で例示されるビニルアルコキシシロキサンポリマーのようなシランカップリング剤
が挙げられる。More specifically, molecular adhesives
Amino group-containing compounds such as triethoxysilylpropylamino-1,3,5-triazine-2,4-dithiol (TES), aminoethylaminopropyl trimethoxysilane;
A triazine compound having a trialkoxysilylalkylamino group such as a triethoxysilylpropylamino group and a mercapto group or an azide group, the following chemical formula (I)

(In formula (I), W may be a spacer group, for example, an alkylene group which may have a substituent, an aminoalkylene group, or a direct bond. Y is an OH group or A reactive functional group that generates an OH group by decomposition or elimination, such as a trialkoxyalkyl group, -Z is -N ₃ or -NR ¹ R ² , provided that R ¹ and R ² are the same or different. H or an alkyl _{^{group, -R 3 Si (R 4)}} m (oR 5) 3-m [R 3, R 4 is an alkyl group, ^{R 5} is H or an alkyl group, m is 0-2. in addition, an alkylene group , An alkoxy group and an alkyl group are each a linear, branched and / or cyclic hydrocarbon group having 1 to 12 carbon atoms which may have a substituent.
A thiol compound having a trialkoxysilylalkyl group;
An epoxy compound having a trialkyloxysilylalkyl group;
Vinyl represented by CH ₂ = CH-Si (OCH ₃ ) ₂ -O- [Si (OCH ₃ ) ₂ -O-] _n -Si (OCH ₃ ) ₂ -CH = CH ₂ (n = 1.8 to 5.7) Examples include silane coupling agents such as alkoxysiloxane polymers.

  Further, molecular adhesives are commercially available silane coupling agents such as vinyltrimethoxysilane (KBM-1003), vinyltriethoxysilane (KBE-1003), as alkoxy group-containing amino group-free silane coupling agents. ) Silane coupling agent containing vinyl group and alkoxy group exemplified by: 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (KBM-303), 3-glycidoxypropylmethyldimethoxysilane (KBM-402) , 3-glycidoxypropyltrimethoxysilane (KBM-403), 3-glycidoxypropylmethyldiethoxysilane (KBE-402), 3-glycidoxypropyltriethoxysilane (KBE-403) Epoxy group and alkoxy group-containing silane coupling agent; styryl group and alkoxy group-containing silane coupling agent exemplified by p-styryltrimethoxysilane (KBM-1403); Acryloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloxypropyltrimethoxysilane (KBM-503), 3-methacryloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloxypropylmethyldiethoxysilane (KBE-503), a (meth) acrylic group and alkoxy group-containing silane coupling agent exemplified by 3-acryloxypropyltrimethoxysilane (KBM-5103); 3-ureidopropyltriethoxysilane (KBE-585) Exemplified ureido group and alkoxy-containing silane coupling agent; 3-mercaptopropylmethyldimethoxysilane (KBM-802), mercapto group exemplified by 3-mercaptopropyltrimethoxysilane (KBM-803) and alkoxy-containing silane coupling Agents: sulfide groups and alkyls exemplified by bis (triethoxysilylpropyl) tetrasulfide (KBE-846) Xi-containing silane coupling agent; isocyanate group exemplified by 3-isocyanatopropyltriethoxysilane (KBE-9007) and alkoxy-containing silane coupling agent (all of which are manufactured by Shin-Etsu Silicone Co., Ltd .; trade names), Further, vinyl group and acetoxy-containing silane coupling agents exemplified by vinyltriacetoxysilane (Z-6075); allyl group and alkoxy-containing silane coupling agents exemplified by allyltrimethoxysilane (Z-6825); methyltrimethoxy Silane (Z-6366), dimethyldimethoxysilane (Z-6329), trimethylmethoxysilane (Z-6013), methyltriethoxysilane (Z-6383), methyltriphenoxysilane (Z-6721), ethyltrimethoxysilane ( Z-6321), n-propyltrimethoxysilane (Z-6265), diisopropyldimethoxysilane (Z-6258), isobutyltri Toxisilane (Z-2306), Diisobutyldimethoxysilane (Z-6275), Isobutyltriethoxysilane (Z-6403), n-hexyltrimethoxysilane (Z-6583), n-hexyltriethoxysilane (Z-6586), Alkyl group and alkoxy group-containing silane coupling agents exemplified by cyclohexylmethyldimethoxysilane (Z-6187), n-octyltriethoxysilane (Z-6341), n-decyltrimethoxysilane (Z-6210); Silane coupling agent containing aryl group and alkoxy group exemplified by methoxysilane (Z-6124); Silane coupling agent containing alkyl group and chlorosilane group exemplified by n-octyldimethylchlorosilane (ACS-8); Tetraethoxysilane (Z-6697) is a silane coupling agent which is an alkoxysilane exemplified by (Z-6697) (all are manufactured by Toray Dow Corning Co., Ltd .; trade name) That.

The amino group-free silane coupling agent having an alkoxy group is a hydrosilyl group (SiH group) -containing alkoxysilyl compound, for example,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₂ OSi (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ H,
(iC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) H ₂ ,
(nC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
(nC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(tC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ Si (CH ₃ ) ₂ H,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(nC ₃ H ₇ ) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(iC ₃ H ₇ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(nC ₄ H ₉ ) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(tC ₄ H ₉ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ H,
(CH ₃ O) ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(CH ₃ O) ₂ CH ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₆ H ₄ OC ₆ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ C ₂ H ₄ Si (CH ₃ ) ₂ H,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p1 Si (CH ₃ ) ₂ H,
C ₂ H ₅ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p2 Si (C ₂ H ₅ ) ₂ H,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ O [Si (CH ₃ ) ₂ O] _p3 Si (CH ₃ ) ₂ H,
(CH ₃ ) ₃ SiOSiH (CH ₃ ) O [SiH (CH ₃ ) O] _p4 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p5 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSiOCH ₃ CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p6 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p7 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ ) SiCH ₃ ] O [SiH (CH ₃ ) O] _p8 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ O [SiH (CH ₃ ) O] _p9 [Si (CH ₃ ) ₂ O] _q1 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _p10 [Si (CH ₃ ) ₂ O] _q2 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [SiH (CH ₃ ) O] _p11 [Si (CH ₃ ) ₂ O] _q3 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiOSi (OC ₂ H ₅ ) ₂ O [SiH (C ₂ H ₅ ) O] _p12 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(Si (OC ₂ H ₅ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _p13 Si (CH ₃ ) ₃ ,
(CH ₃ ) ₃ SiO [(C ₂ H ₅ OSi (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (C ₂ H ₅ )] O [SiH (C ₂ H ₅ ) O] _p14 Si (CH ₃ ) ₃ ,
C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p15 Si (CH ₃ ) ₂ H,
Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p16 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p17 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p18 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p19 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p20 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p21 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p22 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p23 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p24 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p25 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p26 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p27 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p28 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p29 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p30 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p31 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p32 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p33 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p34 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(Si (OCH ₃ ) ₃ CH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ ) Si (CH ₃ ) O] [HSiCH ₃ O] _p35 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [(CH ₃ O) Si (CH ₃ ) CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p36 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _q4 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [Si (OCH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSiC ₆ H ₅ O] _p37 [HSi (CH ₃ ) ₂ OSiC ₆ H ₅ O] _q5 Si (CH ₃ ) ₂ H,
C ₂ H ₅ O (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p38 [SiCH ₃ (C ₆ H ₅ ) O] _q6 Si (CH ₃ ) ₂ H,
Si (OC ₂ H ₅ ) ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p39 [SiCH ₃ (C ₆ H ₅ ) O] _q7 Si (CH ₃ ) ₂ H,
C ₂ H ₅ OSi (CH ₃ ) ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ (CH ₃ ) ₂ SiO [SiH (CH ₃ ) O] _p40 [SiCH ₃ (C ₆ H ₅ ) O] _q8 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO (C ₂ H ₅ O) Si (CH ₃ ) O [SiH (CH ₃ ) O] _p41 [SiCH ₃ (C ₆ H ₅ ) O] _q9 Si (CH ₃ ) ₂ H,
H (CH ₃ ) ₂ SiO [Si (OC ₂ H ₅ ) ₃ CH ₂ CH ₂ CH ₂ Si (CH ₃ )] O [SiH (CH ₃ ) O] _p42 [SiCH ₃ (C ₆ H ₅ ) O] _q10 Si (CH ₃ ) ₂ H
It may be. In these groups, p1 to p42 and q1 to q10 are numbers from 1 to 100. One molecule preferably has 1 to 99 hydrosilyl groups.

An amino group-free silane coupling agent having an alkoxy group is an alkoxysilyl compound containing a hydrosilyl group, for example,
(C ₂ H ₅ O) ₃ SiCH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ (CH ₂ ) ₇ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) OSi (OC ₂ H ₅ ) CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ H ₄ CH = CH ₂ ,
(CH ₃ O) ₂ Si (CH = CH ₂ ) O [SiOCH ₃ (CH = CH ₂ ) O] _t1 Si (OCH ₃ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [SiOC ₂ H ₅ (CH = CH ₂ ) O] _t2 Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t3 CH = CH ₂ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t4 CH = CH ₂ ,
CH ₃ O (CH ₃ ) ₂ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t5 CH = CH ₂ ,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t6 CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ [Si (CH ₃ ) ₂ O] _t7 CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ (- ) O] _u1 Si (CH ₃ ) ₃ CH = CH ₂ ,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ CH ₂ Si (CH ₃ ) ₂ OSi (CH ₃ ) ₂ CH ₂ CH ₂ (Si (CH ₃ ) ₃ O) Si (CH ₃ ) O [SiCH ₃ (- ) O] _u2 [Si (CH ₃ ) ₂ O] _t8 Si (CH ₃ ) ₃ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [SiCH ₃ (OC ₂ H ₅ ) O] _u3 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [Si (OC ₂ H ₅ ) ₂ O] _u4 Si (OC ₂ H ₅ ) ₂ CH = CH ₂ ,
(C ₂ H ₅ O) ₂ Si (CH = CH ₂ ) O [Si (OC ₂ H ₅ ) ₂ O] _u5 Si (OC ₂ H ₅ ) ₂ CH = CH ₂
Is mentioned. In these groups, t1 to t8 and u1 to u5 are numbers from 1 to 30. One molecule preferably has 1 to 30 vinyl groups.

  The reaction between the vinyl group and the SiH group may be promoted with a metal catalyst such as a platinum-containing compound to join the base sheet and the rubber sheet.

As an amino group-free silane coupling agent having an alkoxy group, an alkoxysilyl compound containing an alkoxysilyl group at both ends, for example,
(C ₂ H ₅ O) ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₂ CH ₃ SiCH ₂ CH ₂ Si (OC ₂ H ₅ ) ₃ ,
(C ₂ H ₅ O) ₃ SiCH = CHSi (OC ₂ H ₅ ) ₃ ,
(CH ₃ O) ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₃ (CH ₃ O) ₃ SiCH ₂ CH ₂ C ₆ H ₄ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₃ Si [CH ₂ CH ₂ ] ₃ Si (OCH ₃ ) ₃ ,
(CH ₃ O) ₂ Si [CH ₂ CH ₂ ] ₄ Si (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₂ Si (OC ₂ H ₅ ) ₂ ,
(CH ₃ O) ₂ CH ₃ SiCH ₂ CH ₂ Si (OCH ₃ ) ₂ CH ₃ ,
(C ₂ H ₅ O) ₂ CH ₃ SiOSi (OC ₂ H ₅ ) ₂ CH ₃ ,
(CH ₃ O) ₃ SiO [Si (OCH ₃ ) ₂ O] _v1 Si (OCH ₃ ) ₃ ,
(C ₂ H ₅ O) ₃ SiO [Si (OC ₂ H ₅ ) ₂ O] _v2 Si (OC ₂ H ₅ ) ₃ ,
(C ₃ H ₇ O) ₃ SiO [Si (OC ₃ H ₇ ) ₂ O] _v3 Si (OC ₃ H ₇ ) ₃
It may be. In these groups, v1 to v3 are numbers from 0 to 30.

As an amino group-free silane coupling agent having an alkoxy group, an alkoxysilyl compound containing a hydrolyzable group-containing silyl group, for example,
CH ₃ Si (OCOCH ₃ ) ₃ , (CH ₃ ) ₂ Si (OCOCH ₃ ) ₂ , nC ₃ H ₇ Si (OCOCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCOCH ₃ ) ₃ , C ₆ H ₅ Si ( OCOCH ₃ ) ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si (OCOCH ₃ ) ₃ , CH ₂ = CHCH ₂ Si (OCOCH ₃ ) ₃ , CH ₃ OSi (OCOCH ₃ ) ₃ , C ₂ H ₅ OSi (OCOCH ₃ ) ₃ , CH ₃ Si (OCOC ₃ H ₇ ) ₃ , CH ₃ Si [OC (CH ₃ ) = CH ₂ ] ₃ , (CH ₃ ) ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , nC ₃ H ₇ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₂ = CHCH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , C ₆ H ₅ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₂ = CHCH ₂ Si [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₃ OSi [OC (CH ₃ ) = CH ₂ ] ₃ , C ₂ H ₅ OSi [OC (CH ₃ ) = CH ₂ ] ₃ , CH ₃ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , (CH ₃ ) ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₂ , nC ₃ H ₇ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₂ = CHCH ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , C ₆ H ₅ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₂ = CHCH ₂ Si [ ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₃ OSi [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , C ₂ H ₅ OSi [ON = C (CH ₃ ) C ₂ H ₅ ] ] ₃ , CH ₃ Si [ON = C (CH ₃ ) C ₂ H ₅ ] ₃ , CH ₃ Si [ N (CH ₃ )] ₃ , (CH ₃ ) ₂ Si [N (CH ₃ )] ₂ , nC ₃ H ₇ Si [N (CH ₃ )] ₃ , CH ₂ = CHCH ₂ Si [N (CH ₃ )] ₃ , C ₆ H ₅ Si [N (CH ₃ )] ₃ , CF ₃ CF ₂ CH ₂ CH ₂ Si [N (CH ₃ )] ₃ , CH ₂ = CHCH ₂ Si [N (CH ₃ )] ₃ , CH _It may be a hydrolyzable organosilane such as ₃ OSi [N (CH ₃ )] ₃ , C ₂ H ₅ OSi [N (CH ₃ )] ₃ , CH ₃ Si [N (CH ₃ )] ₃ .

  As an amino group-containing silane coupling agent having an alkoxy group, a commercially available silane coupling agent, specifically N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602), N- 2- (aminoethyl) -3-aminopropyltrimethoxysilane (KBM-603), N-2- (aminoethyl) -3-aminopropyltriethoxysilane (KBE-603), 3-aminopropyltrimethoxysilane ( KBM-903), 3-aminopropyltriethoxysilane (KBE-903), 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine (KBE-9103), N-phenyl-3-amino Amino group-containing alkoxysilyl compound exemplified by propyltrimethoxysilane (KBM-573), N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride (KBM-575) Shin-Etsu Silicone Co., Ltd .; trade name) 3-aminopropyltrimethoxysilane (Z-6610), 3-aminopropyltrimethoxysilane (Z-6611), 3- (2-aminoethyl) aminopropyltrimethoxysilane (Z-6094), 3-phenylaminopropyl Trimethoxysilane (Z-6883), N- [3- (trimethoxysilyl) propyl] -N '-[(ethenylphenyl) methyl-1,2-ethanediamine hydrochloride (Z-6032) Amino group-containing alkoxysilyl compounds (made by Toray Dow Corning Co., Ltd .; trade names).

  Only one of the dry treatment and the molecular adhesive treatment may be applied, or they may be applied alternately and continuously. For example, it may be bonded only by dry processing, may be bonded by molecular adhesive treatment subsequent to dry processing, or may be bonded by molecular adhesion processing subsequent to dry processing and further by dry processing. Moreover, it may be joined only by molecular adhesive treatment, may be joined by dry treatment subsequent to molecular adhesive treatment, or may be joined by dry treatment subsequent to molecular adhesive treatment and further molecular adhesion treatment. .

  As shown in FIG. 2A, the composite heating material 1 of the present invention is a heating element 4 in which a heating member 2 and a current-carrying member 3 are covered with a polymer resin film 6, and the polymer resin film 6 And the heat-radiating rubber insulator layer 5b and the heat-dissipating rubber insulator layer 5b are bonded firmly to each other by the chemical bonding of the active groups on the respective surfaces and molecular adhesion. It may be a thing.

  The heating element 4 of the composite heating material 1 is not particularly limited. In addition to the fiber structure as described above, for example, a thread shape, a wire shape, a film shape, a plate shape, a coil shape, a mesh shape, a mesh shape, a foil shape, It may be a cloth-like, membrane-like or layer-like resistor, and the resistance covering, surrounding, and / or enclosing the resistance, the covering resistance having a woven fabric, non-woven fabric, film material or rubber material, and wiring connected to the resistance May be at least one selected from a flexible heater, a flexible film heater, and a flexible rubber heater.

  Examples of the resistance include those formed of at least one of nickel chromium, iron chromium, copper nickel, copper manganese, conductive resistance ink, and conductive resistance fiber.

  When only a resistor such as a nichrome wire is used as the heating element 4, the heat-dissipating rubber insulator 5 is in direct contact with the nichrome wire, and the contact surface chemically bonds the active groups on the surfaces of each other to bond the molecules. As a result, it joins firmly and becomes a joint surface. Also, when a film heater laminated with a polymer coating or a rubber heater coated with a conductive rubber such as silicone rubber is used, the polymer coating or conductive rubber on the surface contacts the heat-dissipating rubber insulator 5 Then, the contact surfaces are bonded firmly and become bonded surfaces by chemically bonding the active groups on the surfaces of each other and molecular adhesion.

  The shape of the heating element 4 is not particularly limited, and for example, a sheet shape, a sheet shape, a spiral shape, a thread shape, a wire drawing shape, a film shape, a plate shape, a coil shape, a mesh shape, a mesh shape, a foil shape, a fabric shape, and a film shape. And various shapes such as layered.

  As shown in FIG. 2B, the composite heat generating material 1 of the present invention is a composite material in which a plurality of layers each formed of a different rubber material among the rubber materials exemplified in the heat dissipation rubber insulator 5 are laminated. It may have a layer structure. The heat radiation rubber insulator 5 having a multilayer structure includes, for example, a heat radiation rubber insulator layer 5a and a heat radiation rubber insulator layer 5b formed of silicone rubber which are in contact with and bonded to the upper and lower surfaces of the heating element 4. A second heat dissipating rubber insulator layer comprising a heat dissipating rubber insulator layer 5c and a heat dissipating rubber insulator layer 5d formed of EPDM which is in contact with and joined to the surface of the first heat dissipating rubber insulator layer is provided. It is a laminated one. In this way, the heat-dissipating rubber insulator 5 is a composite of at least two layers in which a layered heat-dissipating rubber insulator formed of silicone rubber and a layered heat-dissipating rubber insulator formed of EPDM are laminated. It has a layer structure. As described above, by forming a multilayer structure in which layers formed of rubber materials having different properties are laminated, a plurality of functions can be provided according to the intended use. For example, by forming the heating element 4 having a multilayer structure in which EPDM is laminated on silicone rubber, it is possible to impart gas impermeability that is difficult to develop with silicone rubber alone.

  As shown in FIG. 2C, the composite heat generating material 1 of the present invention has its surface, that is, the surface of the heat radiation rubber insulator 5 comprising the heat radiation rubber insulator layer 5a and the heat radiation rubber insulator layer 5b covering the heat generator 4. The outer surface of the composite heating material 1 may be covered with coatings 7a and 7b made of a resin material or a rubber material.

  Examples of the film formed of a resin material or a rubber material include polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, silicone rubber, and ethylene-propylene-diene-methylene copolymer rubber.

  The composite heat generating material 1 of the present invention exemplifies a material in which the entire heat generating body 4 is insulated and sealed with the heat radiating rubber insulator 5 by molecular adhesion of the heat radiating rubber insulator 5 to all surfaces of the heat generating body 4. However, the heat-dissipating rubber insulator 5 may be molecularly bonded to a part of the surface of the heating element 4. Moreover, as shown in FIG. 3, the heat generating body 4 may be sealed using a heat insulating material 8 together with the heat dissipating rubber insulator 5.

  In the composite heat generating material 1 shown in FIG. 3, the heat radiation rubber insulator 5 is bonded to the surface of the rectangular sheet-shaped heat generating element 4 to which the energizing member 3 is attached by the molecular adhesion exemplified above, and the opposite surface is bonded to the surface. The heat insulating material 8 is bonded by molecular adhesion similar to the molecular bonding exemplified above, and further, the heat insulating rubber insulator 5 and the heat insulating material 8 are similarly bonded by molecular bonding at the contact surface. The heat generating element 4 is sealed by the heat insulating material 8. This composite heat generating material 1 has a planar shape and has different properties on each side. One surface has heat dissipation properties by the heat dissipating rubber insulator 5, and the other surface has heat insulating properties by the heat insulating material 8. it can.

  Examples of the heat insulating material 8 include a foamed body such as a silicone rubber sponge. By the heat insulating material 8, the composite heat generating material 1 can adjust the heat insulating property, and can further improve the tactile sensation.

  The composite heat-generating material 1 of the present invention comprises a heating element 4 and a rubber material or a heat-dissipating rubber insulator 5 that becomes a heat-dissipating rubber insulator 5 directly and / or indirectly through a molecular adhesive under normal pressure. Contacting under pressure or reduced pressure, the contact surface is heated or unheated to form a direct covalent bond with an active group on each surface or an indirect covalent bond via a molecular adhesive, thereby molecular adhesion. It can be manufactured by joining and integrating.

  As a manufacturing method of the composite heat generating material 1 of the present invention, the heat-dissipating rubber insulator 5 and the heat-generating member 4 which are preliminarily molded into an arbitrary shape may be brought into contact with each other, and the rubber material forming the heat-dissipating rubber insulating material 5 is included. Even if the heating element 4 is immersed in the rubber composition or the rubber composition is applied to the heating element 4, the heating element 4 and the rubber material forming the heat-dissipating rubber insulator 5 are brought into contact with each other. Good.

  For example, the heat-generating body 4 is overlapped and brought into contact with the heat-dissipating rubber insulator layer 5a formed into a planar shape, and the heat-dissipating rubber insulator layer 5b is brought into contact with the heat-dissipating rubber insulator layers 5a and 5b. The heat generating body 4 is sandwiched, the contact surface between the heat dissipating rubber insulator layer 5a and the heat generating element 4, the contact surface between the heat dissipating rubber insulating layer 5b and the heat generating element 4, and the heat dissipating rubber insulating layer 5a and the heat dissipating rubber insulating layer 5b. And the contact surface with each other by molecular adhesion exemplified above, the composite heating material 1 in which the heating element 4 is insulated and sealed with the heat-dissipating rubber insulator 5 can be obtained. The molecular adhesion on each contact surface may be performed separately in an arbitrary step, or may be performed collectively as a whole.

  When the heat generating body 4 is planar, the heat generating body 4 and the heat radiating rubber insulator 5 are similarly stacked with the surface heat radiating rubber insulator 5 or the heat radiating rubber insulator 5 on the upper and lower surfaces of the heat generating body 4. 5 may be overlapped and put in contact with each other. When the heating element 4 is coiled, the sheet-like heat-dissipating rubber insulator 5 may be wound around and contacted.

When the heating element 4 and the heat-dissipating rubber insulator 5 are joined and integrated, they may be covalently bonded under normal pressure after being overlapped at normal pressure. And may be covalently bonded by pressure bonding. If necessary, dry treatment such as corona treatment, plasma treatment, or ultraviolet irradiation treatment (general UV treatment or excimer UV treatment) or molecular adhesive treatment is performed on one or both of the bonding surfaces. After the stacking at normal pressure, it may be covalently bonded by pressure bonding under normal pressure, reduced pressure or increased pressure at normal temperature or by heating. Access to the active group such as OH of the heating element 4 and the heat-dissipating rubber insulator 5 or the reactive functional group of the silane coupling agent that reacts with the active group is more specifically 50 torr or less under reduced pressure or vacuum. Is a gas at the contact interface under reduced pressure conditions of 50 to 10 torr, or less than 10 torr, more specifically, less than 10 torr to 1 × 10 ⁻³ torr, preferably less than 10 torr to 1 × 10 ⁻² torr. This is facilitated by removing the medium or by heating the contact interface by applying stress (load), for example 10-200 kgf, to the contact interface. It is preferable that pressure is uniformly applied to the entire joining surface of the heat generator and the heat-dissipating rubber insulator under reduced pressure or pressurized conditions. If it is out of the above range, the pressure may not be applied uniformly.

  When the heat-dissipating rubber insulator 5 is made of silicone rubber, the active group can be expressed directly by corona treatment, plasma treatment or ultraviolet irradiation treatment (general UV treatment or excimer UV treatment). Although it may join, you may join using molecular adhesives, such as the said silane coupling agent. On the other hand, when the heat-dissipating rubber insulator 5 is formed of a rubber material other than silicone rubber, it is dipped in a 0.05 to 1% by weight alcohol solution such as a methanol solution of a molecular adhesive such as the silane coupling agent and dried. Then, it is preferable to be joined. If the concentration of the molecular adhesive solution is too high, the bonding surface between the heating element 4 and the heat-dissipating rubber insulator 5 will be peeled off, and if it is too thin, the heating element 4 and the heat-dissipating rubber insulator 5 cannot be sufficiently bonded. End up.

  Examples of the present invention will be described in detail below, but the scope of the present invention is not limited to these examples.

Example 1
A heating wire, which is a nichrome wire as a heating element, is subjected to corona discharge treatment as a surface treatment to generate a hydroxyl group on the heating wire, and (CH ₂ = CH-) (CH ₃ O-) ₂ Si-O-[(CH ₂ = CH-) (CH ₃ O-) Si-O] _n1 -Si (-OCH ₃ ) ₂ (-CH = CH ₂ ) (n1 = 1 to 30) The vinyl-containing silyl compound was reacted with the hydroxyl group on the heating wire by heat treatment. It was immersed in a platinum-containing catalyst, specifically a hexane solution of a platinum complex such as a platinum-tetramethyldivinyldisiloxane complex, and dried to obtain a heating element having a platinum-containing catalyst on the surface. Although the chemical structure is not necessarily clear, it is assumed that the platinum atom of the platinum complex is coordinated to a plurality of vinyl-containing silyl groups generated on the surface of the heating wire. On the surface of this heating wire, 50 parts by weight of SH1005 (made by Toray Dow Corning Co., Ltd .; trade name) which is methyl vinyl silicone rubber as silicone rubber, and SH200 100cs (Toray Dow Corning) which is polydimethylsiloxane as silicone oil. 50 parts by weight of a product manufactured by Co., Ltd .; trade name), and 50 parts by weight of Pyroxma 5301 (product of Kyowa Chemical Industry Co., Ltd .; product name, average particle size 2 μm), which is magnesium oxide as a thermally conductive filler, and Pyroxma 3320 (Kyowa Chemical). 200 parts by weight of Kogyo Co., Ltd .; trade name, average particle size 20 μm) and 50 parts by weight of Heidilite H32 (made by Showa Denko KK; trade name), which is aluminum hydroxide Al (OH) ₃ as an additive, and VESTA PP (Inoue Lime Industry Co., Ltd.) which is calcium oxide CaO 10 parts by weight of the product (trade name) and 0.01 parts by weight of a platinum carbonylcyclovinylmethylsiloxane complex vinylmethyl cyclic siloxane solution which is a platinum complex (manufactured by GELEST) as a platinum catalyst were obtained. A rubber composition for a heat-dissipating rubber insulator was applied, heated under pressure, and cured. Then, the hydrosilyl group of the hydrosilyl group-containing polysiloxane undergoes a hydrosilylation reaction to the double bond of the vinyl-containing silyl group preferentially over the cross-linking polymerization of the vinyl-containing silyl groups, thereby increasing the molecular weight, and the surface of the heating wire. On top of this, a heat generating silicone rubber insulator made of polysiloxane was coated and bonded to obtain a composite heating material.

  In addition, a composite using these various heating elements under the same conditions and method as described above except that a cloth-like planar heating element, a silicone rubber heater, and a film heater were used instead of the heating wire as the heating element. Each heat generating material was produced.

(Comparative Example 1)
On the surface of a heating wire which is a nichrome wire as a heating element, 50 parts by weight of SH1005 (product name) manufactured by Toray Dow Corning Co., Ltd. as a silicone rubber, and SH200 which is polydimethylsiloxane as a silicone oil. 50 parts by weight of 100 cs (manufactured by Toray Dow Corning Co., Ltd .; trade name) and 50 parts by weight of Pyroxma 5301 (trade name, average particle size 2 μm), which is magnesium oxide as a thermally conductive filler. And 200 parts by weight of Pyroxuma 3320 (manufactured by Kyowa Chemical Industry Co., Ltd .; trade name, average particle size 20 μm) and Heidilite H32 (made by Showa Denko KK; trade name) which is aluminum hydroxide Al (OH) ₃ as an additive ) VESTA P which is 50 parts by weight of calcium oxide and CaO 10 parts by weight of P (made by Inoue Lime Industry Co., Ltd .; trade name) and 0.01 parts by weight of a platinum carbonylcyclovinylmethylsiloxane complex vinylmethyl cyclic siloxane solution which is a platinum complex (manufactured by GELEST) as a platinum catalyst. Applying the rubber composition for the heat radiation rubber insulator obtained by kneading, pressurizing and heating, and curing, the heating element that is a heating wire and the heat radiation rubber insulator that is a heat radiation silicone rubber insulator are simply A composite heat generating material adhered and adhered was obtained.

  Further, these heating elements and heat-dissipating silicone rubber were used under the same conditions and methods as above except that a cloth-like sheet heating element, a silicone rubber heater, and a film heater were used instead of the heating wire as the heating element. The composite heat generating materials were prepared by simply adhering the insulating rubber insulator, which is an insulator, in close contact with each other.

(Comparative Example 2)
An adhesive (trade name, manufactured by Cemedine Co., Ltd.) comprising a heat-dissipating silicone rubber insulator formed of silicone rubber preliminarily cured under the same conditions as in Example 1 and Comparative Example 1, and a heating wire which is a nichrome wire as a heating element; A cemented exothermic material was obtained using Cemedine No. 8008).

  Further, these heating elements and heat-dissipating silicone rubber were used under the same conditions and methods as above except that a cloth-like sheet heating element, a silicone rubber heater, and a film heater were used instead of the heating wire as the heating element. Composite heat generating materials were prepared by bonding a heat-dissipating rubber insulator as an insulator with an adhesive.

(Adhesive strength evaluation)
The composite heating material obtained in Example 1, Comparative Example 1 and Comparative Example 2 was used with a width of 10 mm in a state where a pulling margin of about 3 cm was introduced in advance. The tensile tester used was a digital force ZP-200N manufactured by Imada Co., Ltd. installed on a vertical electric measurement stand MX2-1000N. The heating element part of the composite heating material produced was sandwiched between the lower grips of the stage of the tensile tester, and the heat-dissipating rubber insulator part was sandwiched between the upper grips and peeled at a gripping movement speed of 100 mm / sec and an angle of 180 °. The state of peeling at that time was recorded. In addition, they were bonded without being peeled, and when the bonded rubber was broken, the broken state of the rubber and the maximum peel strength were recorded. The evaluation results are shown in Table 1 below.

(Heat resistance evaluation)
The composite heating material obtained in Example 1, Comparative Example 1 and Comparative Example 2 was used with a width of 10 mm in a state where a pulling margin of about 3 cm was introduced in advance. A thermal shock test was conducted using a small thermal shock device TSE-11-A manufactured by ESPEC Corporation. The thermal shock test was performed by repeating 100 cycles of holding for 30 minutes in a temperature environment of −40 ° C. and 80 ° C., respectively. After the test, a tensile test similar to the adhesive strength evaluation was performed, and the maximum peel strength and peel state were recorded. The evaluation results are shown in Table 1 below.

(Bend resistance test)
The composite heating material obtained in Example 1, Comparative Example 1 and Comparative Example 2 was used with a width of 10 mm. A torsion test was performed using a small desktop durability tester TCDMLH-FT manufactured by Yuasa System Equipment Co., Ltd. The test was conducted at room temperature, with a twist angle of 90 degrees, a speed of 90 rpm, and a cycle number of 1000, and it was confirmed whether or not peeling occurred in the composite after the test. The evaluation results are shown in Table 1 below.

  According to the adhesive strength test, the composite heating material of Example 1 has an adhesive strength that causes the rubber material to cohesively break without peeling at the interface between the various heating elements and the heat-dissipating rubber insulator in all the heating elements. Became clear. On the other hand, the composite heating material of Comparative Example 1 was peeled off at the bonding surface between the heating element and the heat-dissipating rubber insulator that were bonded by simply contacting them. The composite heating material of Comparative Example 2 was confirmed to have substantially the same adhesive strength as that of the example.

  According to the heat resistance test, the composite heat generating material of Example 1 was bonded to such a degree that the rubber material cohesively breaks without peeling off at the interface between the various heat generating elements and the heat-dissipating rubber insulator even after all the heat generating elements were tested. It was found to have strength. The composite heating material of Comparative Example 1 was peeled off at the bonding surface between the heating element and the heat-dissipating rubber insulator that were bonded by simply contacting them. It was confirmed that the adhesive strength of the composite heat generating material of Comparative Example 2 was clearly reduced.

  As a result of the bending resistance test, the composite heat generating material of Example 1 was not confirmed to be peeled even after all the heating elements were tested. Comparative Example 1 and Comparative Example 2 were peeled off during the test.

(Thermal conductivity evaluation)
A voltage suitable for each heating element is applied to each composite heating material produced in Example 1 and Comparative Examples 1 and 2 using a voltage regulator MVS-2000 (manufactured by Yamahishi Electric Co., Ltd .; trade name), The surface temperature shift was recorded. The memory shift was recorded using a Memory Hilogger LR8431 (manufactured by Hioki Electric Co., Ltd .; trade name). The surface temperature of the composite heating material from the voltage application to 1,000 seconds later was measured.

  The measurement result of each composite heat generating material produced in Example 1 and Comparative Examples 1-2 is shown in FIG. In FIG. 4, the heating wire is heated by applying a voltage of 2 V, and the surface temperature of the heat radiating rubber insulator is measured. FIG. 4 (a), the fabric heating element is heated by applying a voltage of 100 V, The surface temperature of the heat-dissipating rubber insulator was measured, and the result was shown in FIG. 4B. The result of measuring the surface temperature of the heat-dissipating rubber insulator was shown in FIG. The results of measuring the surface temperature of the heat-dissipating rubber insulator by applying a voltage of 100V to the heater and heating are shown in FIG.

  As a result of the thermal conductivity test, the composite heating material of Example 1 was bonded by close contact, so that Comparative Example 1 having an air layer at the interface between the heating element and the radiating rubber insulator, Compared to Comparative Example 2 with an adhesive layer at the interface, the slope of the graph of thermal change is larger, the temperature is higher in a short time, and the heat conduction efficiency from the heating element to the heat dissipation rubber insulator is excellent It became clear that

  The composite heating material of the present invention is used for snow melting, anti-freezing and heating, for example, for building materials such as roofing materials, wall materials, flooring materials, piping materials, furniture, etc. Also useful.

  1 is a composite heat generating material, 2 is a heat generating member, 3 is an energizing member, 4 is a heating element, 5 is a heat radiating rubber insulator, 5a, 5b, 5c and 5d are heat radiating rubber insulating layers, 6 is a polymer resin film, 7a 7b is a coating, and 8 is a heat insulating material.

Claims (11)

  The heat-dissipating rubber insulator and at least a part of the heating element are joined and integrated by an active group on the surface of each other directly and / or indirectly through a molecular adhesive. Characteristic composite heating material.   The heat radiating rubber insulator and the heating element are formed on the surface by at least any one of a dry treatment selected from a corona treatment, a plasma treatment, and an ultraviolet irradiation treatment and a molecular adhesive treatment by the covalent bond. The composite heating material according to claim 1, wherein the composite heating material is joined and integrated.   The heating element covers, surrounds, and / or encloses the resistance in the form of a thread, wire, film, plate, coil, mesh, mesh, foil, fabric, film or layer, or the resistance. At least one heater selected from a flexible heater, a flexible film heater, and a flexible rubber heater having a covering resistance having a woven fabric, a non-woven fabric, a film material or a rubber material, and a wiring connected to the resistance The composite heating material according to claim 1, wherein the composite heat generating material is provided.   The composite heating material according to claim 3, wherein the resistance is formed of at least one of nickel chrome, iron chrome, copper nickel, copper manganese, conductive resistance ink, and conductive resistance fiber.   The composite heating material according to claim 1, wherein the heating element has a planar shape.   The composite heating material according to claim 1, wherein the heating element is coated with a polymer resin.   2. The heat radiation rubber insulator is formed of at least one rubber material selected from silicone rubber, ethylene-propylene-diene-methylene copolymer rubber, urethane rubber, and fluorine rubber. The composite heating material described in 1.   The composite heat generating material according to claim 7, wherein the heat radiation rubber insulator has a multilayer structure formed of the rubber material.   2. The composite heat generating material according to claim 1, wherein the heat dissipating rubber insulator is covered with a film made of a resin material or a rubber material.   The heat-dissipating rubber insulator is bonded to one surface of the heating element by the covalent bond, and the heat insulating material is bonded to the other surface directly on the surface of each other and / or indirectly through a molecular adhesive. The composite heating material according to claim 1, wherein the composite heating material is integrated by being bonded by a simple covalent bond. A heating element and a rubber material or a heat radiation rubber insulator to be a heat radiation rubber insulator are brought into contact with each other directly and / or indirectly through a molecular adhesive under normal pressure, pressure or reduced pressure. Forming a direct covalent bond at the active group on the surface and / or indirectly via the molecular adhesive,
A method of manufacturing a composite heating material, wherein at least a part of the heating element and the heat-dissipating rubber insulator are joined and integrated by the covalent bond.

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