JP2009045799A - Multilayer laminated body and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated body having strong thermal-shock resistance and excellent adhesion. <P>SOLUTION: This invention relates to the multilayer laminated body and its manufacturing method. The multilayer laminated body comprises: at least one of a metallic layer and a resin layer; and an elastic electric insulation layer, wherein the metallic layer and/or the resin layer is adhered to the elastic electric insulation layer. The elastic electric insulation layer is composed of an unsaturated carboxylic acid-grafted denatured polyolefin. The unsaturated carboxylic acid-grafted denatured polyolefin does not contain gels insoluble in xylene that is heated to 140°C. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a multilayer laminate and a method for producing the same.

  Thermosetting resin compositions such as polysiloxane compositions containing fillers, polyvinylidene fluoride compositions, and epoxy resin compositions are known as coating materials applied to metal substrates that require an insulating protective coating. ing.

  However, since these thermosetting resin compositions generally require a curing time of several tens of units for the curing reaction, the polysiloxane composition (silicone-based curing material) is inferior in workability, and the cost is high. Epoxy resin compositions are inexpensive, but are vulnerable to changes in environmental temperature, and have problems such as material destruction due to thermal shock and peeling from the adherend.

  On the other hand, when an engineering plastic such as polyimide is used as the metal insulator, it is extremely difficult to satisfy the insulating properties, the adhesive strength with the metal, the mechanical strength such as bending and impact at the same time. In addition, similar to the epoxy resin composition, it cannot follow a rapid temperature change such as a heat shock, and the adhesive layer is broken and the function as an electronic component is impaired.

  Therefore, it is relatively easy to manufacture, and can be easily and strongly performed by a simple method that can be easily automated by means such as continuous lamination, and at a relatively low temperature in a short time without special treatment on the metal surface. There has been a need for an insulating elastic layer that can be thermally bonded to a metal substrate, that is, an elastic sheet, an elastic film, an elastic tape, or the like.

  Polyolefin is suitable as an inexpensive material with excellent electrical insulation. However, when used as a laminate, polyolefin is a nonpolar polymer, so its adhesion to various polar substances is low and its adhesion to metals is extremely high. There is a problem that it is low.

  Therefore, various studies for improving the adhesiveness have been made in order to use an inexpensive polyolefin having excellent moldability as a thermally adhesive insulating material. As one of the methods, for example, a modified polyolefin resin grafted with an unsaturated carboxylic acid or a derivative thereof has been proposed (Patent Document 1).

  This technology is to produce a polyolefin grafted with an unsaturated carboxylic acid by dissolving the polyolefin in a solvent and grafting the unsaturated carboxylic acid. As a solvent, aliphatic hydrocarbons such as pentane, hexane, heptane, benzene, Aromatic hydrocarbons such as toluene and xylene are used.

  However, these aromatic hydrocarbons have a relatively high boiling point, the reaction temperature is as high as 160 ° C., and the energy cost is high, and there is a possibility that the cost is high in the recovery process. Also, it is desired that benzene and the like are not used as carcinogenic substances from the viewpoint of toxicity. On the other hand, aliphatic hydrocarbons such as hexane cannot be said to have sufficient solubility of polyolefin, and it is necessary to increase the melting temperature, which is a high-cost manufacturing process.

  Further, it is known to produce an unsaturated carboxylic acid grafted polyolefin by grafting an unsaturated carboxylic acid in a melted state of the polyolefin, and a method using an extruder is generally used as this method, for example, The method using the twin-screw extruder which has a vent port is mentioned (patent document 2).

  However, in the melting method, the residence time in the extruder, that is, the graft reaction time is limited, and it is difficult not only to react a sufficient amount of the unsaturated carboxylic acid, but also a local reaction is unavoidable. As a result, the graft reaction became non-uniform, and the generation of gels and fish eyes was induced in terms of quality. In addition, it is necessary to carry out the reaction at a resin temperature as high as 250 ° C., and it is necessary not only to introduce the unsaturated carboxylic acid more than necessary by the sublimation, volatilization and evaporation of the unsaturated carboxylic acid, Since the amount of grafting to the saturated carboxylic acid grafted polyolefin is small, it cannot be said that the adhesiveness is sufficient as a metal insulating material, and a material with further improved adhesiveness has been desired.

  That is, the unsaturated carboxylic acid grafted polyolefin obtained by these conventional production processes has a problem that it has low thermal stability and contains a gel. In addition, although the adhesiveness is improved as a metal insulating resin, when used as an adhesive layer for laminating two different materials, for example, metal and plastic, the resulting laminate is less susceptible to thermal shock and more elastic. Insulating resin which is rich in and excellent in adhesiveness has been demanded.

Japanese Patent Laid-Open No. 9-3138 JP 2002-187914 A

  This invention is made | formed in view of said subject, The objective is to provide the laminated body strong to a thermal shock and excellent in adhesiveness.

  As a result of intensive studies, the present inventors have found that a layered product produced from a specific polyolefin grafted with an unsaturated carboxylic acid, that is, a film, a sheet, or a tape, is heated for a short time under pressure at a relatively low temperature. A multilayer laminate composed of at least one of a metal layer and a resin layer and an elastic electrical insulating layer can be manufactured by utilizing the fact that it adheres firmly to a metal layer or the like and has excellent elastic properties. Since the metal layer and / or the resin layer and the elastic electrical insulating layer are bonded to each other, the present inventors have found that a multilayer laminate having excellent thermal shock resistance that is difficult to achieve with a thermosetting resin can be provided. That is, the present invention is a multilayer laminate composed of at least one of a metal layer and a resin layer and an elastic electrical insulation layer, wherein the metal layer and / or the resin layer and the elastic electrical insulation layer are bonded, A multilayer laminate comprising an elastic electrical insulating layer made of a modified polyolefin grafted with an unsaturated carboxylic acid, and the modified polyolefin grafted with the unsaturated carboxylic acid does not contain a gel insoluble in xylene heated to 140 ° C. And its manufacturing method.

  Hereinafter, the present invention will be described in detail.

  The multilayer laminate of the present invention is composed of at least one of a metal layer and a resin layer and an elastic electrical insulation layer, and there is no limitation as long as the metal layer and / or the resin layer and the elastic electrical insulation layer are bonded. A multilayer laminate composed of at least one of a metal layer and a resin layer can be formed by taking advantage of the strong adhesion of the elastic electrical insulating layer to the metal layer.

  The multi-layer laminate of the present invention includes, for example, a two-layer laminate of metal layer / elastic electric insulation layer, resin layer / elastic electric insulation layer, metal layer / elastic electric insulation layer / resin layer, metal layer / elasticity. Three-layer laminates such as electrical insulation layer / metal layer, metal layer / elastic electrical insulation layer / metal layer / elastic electrical insulation layer, metal layer / elastic electrical insulation layer / resin layer / elastic electrical insulation layer, resin layer / elasticity A four-layered laminate such as an electrical insulating layer / metal layer / elastic electrical insulating layer is exemplified, but these examples do not limit the present invention, and a multilayered laminate can be formed. .

  In addition, the thickness of each layer is not limited as long as heat bonding is possible, and the same applies to a metal layer or a resin layer that is not flat and has unevenness formed by stacking circuits formed of a metal material. . Further, the metal layer is not in a state where the entire surface of the layer is covered with the metal layer, but a layer having a surface composed of a resin layer and a metal layer can be similarly formed into a laminate.

  The metal layer in the multilayer structure of the present invention is a flat planar metal molded body such as a metal foil, film, sheet or plate, and a three-dimensional shape obtained by further secondary processing of the molded body. The two-dimensional or three-dimensional molded body may be a rectangular shape or may have a complicated planar shape like an electronic circuit. . For this reason, when a layer is not a plane, it may have a surface with a specific and non-constant curvature. Here, examples of the metal include steel, copper, aluminum, tin-plated aluminum, silver-plated copper, polished stainless steel, and blasted steel. Furthermore, the present invention can be similarly applied to a metal whose surface is plated with a different metal.

  The resin layer in the multilayer structure of the present invention includes a flat planar molded body such as a thin film, a film, a sheet, and a plate made of thermoplastic resin, thermosetting resin, injection molding, extrusion molding, This is a general term for various three-dimensional shaped articles obtained by mold molding and the like, and usually by methods used for resin molding. There is no restriction | limiting in the shape of these molded objects, The thing of arbitrary shapes is included. For this reason, when a layer is not a plane, it may have a surface with a specific and non-constant curvature. Here, examples of the thermoplastic resin include polyimide, polyamide, polycarbonate, polyphenylene sulfide, and the like, and examples of the thermosetting resin include an epoxy resin, a phenol resin, and a silicone resin.

  The elastic electrical insulating layer in the multilayer laminate of the present invention is a layer that can be hot-melt bonded to a metal layer or the like, and is composed of a modified polyolefin grafted with an unsaturated carboxylic acid (hereinafter referred to as an unsaturated carboxylic acid grafted polyolefin). It is. When the elastic electrical insulating layer is made of an unsaturated carboxylic acid grafted polyolefin, a laminate having excellent insulating properties, thermal shock properties, and adhesive strength can be produced.

  The unsaturated carboxylic acid grafted polyolefin does not contain a gel insoluble in xylene heated to 140 ° C. Including a gel insoluble in xylene heated to 140 ° C. not only greatly deteriorates the appearance of the product when it is formed into a film, but also depending on the amount of the gel, mechanical properties such as adhesive strength and durability are deteriorated and peeled off. Such problems arise.

  The amount of the unsaturated carboxylic acid grafted polyolefin of the unsaturated carboxylic acid grafted polyolefin is not particularly limited, but preferably 0.1 to 10% by weight in order to have sufficient adhesiveness and to maintain the melt viscosity of the polyolefin moderately. More preferably, it is 0.5 to 8% by weight.

  The unsaturated carboxylic acid grafted polyolefin is in accordance with the type of raw material polyolefin as described later, for example, unsaturated carboxylic acid grafted polyethylene, unsaturated carboxylic acid grafted ethylene / propylene copolymer, unsaturated carboxylic acid grafted ethylene / butene copolymer. And unsaturated carboxylic acid grafted ethylene / hexene copolymer, unsaturated carboxylic acid grafted ethylene / vinyl acetate copolymer, and unsaturated carboxylic acid grafted polypropylene.

  Examples of the unsaturated carboxylic acid include unsaturated monocarboxylic acids and derivatives thereof, unsaturated dicarboxylic acids and derivatives thereof, and acid anhydrides and derivatives of unsaturated dicarboxylic acids. Examples of unsaturated monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, and the like. Derivatives of unsaturated monocarboxylic acids include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl ( Examples include meth) acrylate, isopropyl (meth) acrylate, and butyl acrylate. Examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, itaconic acid, citraconic acid, and tetrahydrophthalic acid. Desaturated dicarboxylic acids include monomethyl maleate, dimethyl maleate, monoethyl maleate, and maleic acid. Examples include diethyl, monomethyl fumarate, dimethyl fumarate, monoethyl fumarate, and diethyl fumarate. Examples of the acid anhydrides of unsaturated dicarboxylic acid and derivatives thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride and the like. These may be used alone or in combination of two or more. In particular, from the viewpoint of adhesiveness, maleic anhydride alone or a combination of maleic anhydride and (meth) acrylic acid esters is preferable.

  Examples of the polyolefin include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (L-LDPE), and very low density polyethylene (V-LDPE). It is done. Examples of linear low density polyethylene (L-LDPE) include ethylene-α-olefin copolymers such as ethylene-1-butene copolymer, ethylene-1-hexene copolymer, and ethylene-1-octene copolymer. Can be mentioned. Other ethylene copolymers such as ethylene-4-methylpentene-1 resin, ethylene-vinyl acetate copolymer (EVA) and saponified products thereof, ethylene-vinyl alcohol resin (EVOH), ethylene-propylene copolymer (EPM), etc. , Polypropylene homopolymer, polypropylene block copolymer, polypropylene random copolymer, and the like, and chlorinated products of these polyolefins can be used in the same manner.

  The polymerization method for synthesizing these polyolefins may be a generally known method, including high-pressure radical polymerization, medium-low pressure polymerization, solution polymerization, slurry polymerization, etc., and the catalyst used is a peroxide catalyst, Ziegler-Natta. Examples of the catalyst include metallocene catalysts, and polyolefins polymerized with these catalysts can be used.

  The melt mass flow rate (MFR) that is a measure of the molecular weight of the polyolefin is not particularly limited, but it is preferable in order to make the solubility in a solvent good even when heated and to maintain the material strength of the final graft reaction product. It is 0.01-50000 (g / 10min), More preferably, it is 0.01-100 (g / 10min).

  Methods for chlorinating polyolefins are known. For example, a method of chlorinating polyolefins by bringing a solution dissolved in a halogen-based solvent such as carbon tetrachloride into contact with a chlorine-containing gas under ultraviolet irradiation (for example, JP 47-8643), a method of chlorinating olefins by blowing chlorine gas into a slurry in which polyolefin powder is suspended in water (for example, Japanese Examined Patent Publication No. 36-4745), a polyolefin without using a solvent. Is heated above its melting point and brought into contact with chlorine gas in a molten state, whereby a polyolefin is chlorinated without using a radical generator, ultraviolet irradiation or the like (for example, JP-A-3-199206) Is disclosed. The chlorinated polyolefin used in the present invention can be produced by any of these methods, and the production method of the chlorinated polyolefin is not limited.

  The unsaturated carboxylic acid grafted polyolefin used in the multilayer laminate of the present invention can be produced by grafting an unsaturated carboxylic acid onto the polyolefin using a radical generator in a halogen-based solvent. Examples of the halogen solvent include 1,1,2-trichloroethane, chloroform, carbon tetrachloride and the like. When 1,1,2-trichloroethane is used as the halogen-based solvent, commercially available 1,1,2-trichloroethane often contains 0.5 to 2.0% by weight of an alcohol compound and / or an epoxy compound. Is contained as an impurity. Here, the alcohol compound is a compound having a hydroxyl group, and examples thereof include ethyl alcohol and butyl alcohol. The epoxy compound is a compound having an epoxy group, such as 1,2-epoxypropane and 1,2 -Epoxybutane etc. are mentioned. In order to obtain an unsaturated carboxylic acid grafted polyolefin which is colorless and transparent, has good thermal stability and does not contain a gel, when 1,1,2-trichloroethane is used as a solvent, 1 It is preferable to remove in advance the alcohol compound and / or epoxy compound contained as impurities in the 1,2-trichloroethane.

  As the radical generator, an azo compound or an organic peroxide is used. Examples of the azo compound include α, α-azobisisobutyronitrile, azobiscyclohexanecarbonitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), and the organic peroxide includes Examples include benzoyl peroxide, acetyl peroxide, t-butyl peroxide, and t-butyl perbenzoate.

  The amount of azo compound or organic peroxide added is not particularly limited, but the product maintains the graft amount of unsaturated carboxylic acid and prevents increase in melt viscosity of the resin to prevent deterioration of moldability. In order to maintain the quality, the amount is preferably 0.05 to 5 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the polyolefin.

  The reaction temperature is not particularly limited, but is preferably 40 to 130 ° C., more preferably 60 to 130 ° C. in order to increase the efficiency of the graft reaction and prevent coloring and crosslinking of the modified polyolefin. The reaction pressure is not particularly limited, but is preferably 0 to 1 MPa, more preferably 0 to 0.7 MPa, in order to graft a sufficient amount of unsaturated carboxylic acid and to suppress the generation of gel to prevent deterioration of quality. is there. In this reaction, depending on the reaction temperature and the type of polyolefin to be reacted, the grafting reaction proceeds from a uniform solution state to a suspended state, but the grafting reaction proceeds in the uniform solution state as much as possible. It is preferable to select the temperature appropriately.

  After completion of the grafting reaction, a stabilizer is added as necessary. Stabilizers are preferably added to eliminate radicals generated during the grafting reaction and stop the grafting reaction. It is preferable to use an antioxidant that is usually added to the polyolefin. For example, a phenolic antioxidant or a phosphorus antioxidant. , Sulfur-based antioxidants, and composite antioxidants thereof are preferably used.

  As the reaction vessel used for the grafting reaction, a vessel used for a batch-type reaction can be used. Any material can be used as long as it can withstand the above reaction temperature and reaction pressure, and the material is usually made of stainless steel. If necessary, it is possible to use a glass lining and fluorine coating treated on the inner surface.

  In order to separate the unsaturated carboxylic acid grafted polyolefin produced by the graft reaction from the solvent, a commonly used method such as a drum dryer, steam distillation, or an extruder with a vent can be used, but it is economical to use a drum dryer. It is particularly preferable from the viewpoint of practical use.

  When using a drum dryer as a method for separating the unsaturated carboxylic acid grafted polyolefin from the solvent in the reaction step, after the reaction step, the reaction solution is continuously fed from the reactor to a heated drum dryer. The product is isolated from the polymer solution. The temperature of the drum dryer at this time is preferably in the range of 120 to 200 ° C., more preferably 150 to 165 ° C. in order to suppress the coloring, thermal deterioration and crosslinking of the polymer while promoting drying. The polymer is a thin film that is peeled off from the drum and isolated.

  Further, 1,1,2-trichloroethane volatilized by the drum dryer can be recovered by using a recovery line installed at the upper part of the drum dryer and used again for the reaction.

  The time required for removing the solvent from the polymer solution by the drum dryer varies depending on the type of the solvent to be used and the temperature of the drum dryer, and can be appropriately selected, but is usually 10 seconds to 5 minutes.

  The isolated polymer can be processed into strings, sheets, strands or chips as required, and these primary shaped polymers can be further uniaxially or biaxially extruded as required. It is also possible to feed to a machine, melt and extrude the polymer, and pelletize by strand cutting or underwater cutting. The extrusion temperature in this case is not particularly limited, but is preferably 100 to 300 ° C., more preferably 150 to 300 ° C. in order to sufficiently melt the used polyolefin and smoothly extrude it, and to further suppress the decomposition and coloring of the polyolefin. 250 ° C.

  Other resins can be blended with the unsaturated carboxylic acid grafted polyolefin. Examples of the other resin include not only the above-mentioned polyolefin resin not subjected to graft reaction, but also styrene resins such as polystyrene, poly-α-methylstyrene, polystyrene-acrylonitrile copolymer, styrene-acrylonitrile-butadiene resin, poly Acrylic resins such as acrylic acid and polymethacrylic acid-methyl, polyvinyl chloride resins, polyvinylidene chloride resins, polyamides, polyesters, polycarbonate resins, fluorine resins, silicone resins, polyphenylene oxide resins (PPO), polyphenylene sulfide resins (PPS), polyimide, polysulfone, polyethersulfone, polyether-etherketone, polybutylene terephthalate resin (PBT), polyoxymethylene resin (POM), epoxy resin Polyurethanes, urea resins, phenol resins, melamine resins, cellulose, and petroleum resins. If necessary, it is possible to chemically react a reactive functional group or other resin having a terminal group with the unsaturated carboxylic acid group of the present invention, utilizing the physical interaction between these functional groups. Blending is possible. Furthermore, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added as a third component to improve compatibility with other resins, or to improve adhesiveness.

  An elastomer or a rubber component can be blended with the unsaturated carboxylic acid grafted polyolefin. Examples of the elastomer or rubber component include natural rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, butyl rubber, ethylene-propylene rubber, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, epichlorohydrin rubber, nitrile rubber, and acrylic rubber. , Urethane rubber, silicone rubber, fluorine rubber and the like. In addition, as thermoplastic elastomer (TPE), SBS, SIS and other styrene TPE (SBC), polyolefin TPE (TPO), urethane TPE (TPU), polyester elastomer (TPEE), polymeramide elastomer (TPA), Examples include silicone-based TPE and fluorine-based TPE.

  The following various additives can be mix | blended with unsaturated carboxylic acid graft polyolefin. Examples of the antioxidant include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and composite antioxidants thereof. Other stabilizers include organic phosphite stabilizers, thioether stabilizers, hindered amine light stabilizers, and the like. Moreover, as a filler, a spherical filler, a plate-like filler, a fibrous filler etc. are mentioned, for example. Examples of the adhesive include liquid and solid bisphenol A epoxy resin, epoxy cresol novolak, epoxy phenol novolak and a mixture of bisphenol A epoxy resin and epoxy cresol novolak or epoxy phenol novolak, bisphenol F epoxy resin, aliphatic epoxy resin, and the like. Can be mentioned. Examples of the epoxy crosslinking agent include boron trifluoride complex compounds, dicyandiamide, polyamides, and polyamines. Examples of the flame retardant include brominated flame retardants such as ethylene bistetrabromophthalimide, decabromodiphenyl oxide, SAYTEX 8010, tetradecabromodiphenoxybenzene, antimony trioxide, antimony pentoxide, zinc borate, FIREBRAKE ZB, and the like. Flame retardant aids, chlorinated flame retardants such as DECLORONE PLUS, and the like. As a lubricant, higher fatty acid metal salts such as magnesium salts of higher fatty acids such as stearic acid, oleic acid, lauric acid, alkaline earth metal salts such as calcium salts and barium salts, cadmium salts, zinc salts, lead salts, and Alkali metal salts such as sodium salt, potassium salt and lithium salt can be used. Other additives include antistatic agents, colorants, natural oils, synthetic oils, waxes, plasticizers, nucleating agents, heavy metal deactivators, processing aids, waxes, arc inhibitors, alumina, silane treatment And dripping inhibitors such as talc, mica, feldspar and wollastonite. The addition amount of the additive is not particularly limited, but 20 parts by weight to 40 parts by weight with respect to 100 parts by weight of the unsaturated carboxylic acid grafted polyolefin in order to develop the additive effect of the additive and maintain adhesiveness. Part.

  For mixing unsaturated carboxylic acid grafted polyolefin and other resins, elastomer or rubber components, and various additives, commonly used kneading methods can be used. Single screw extruder, twin screw extruder, Brabender internal mixer, Banbury A mixer, roll, kneader, Henschel mixer, V blender, tumbler mixer, or the like can be used.

  The electroelastic insulating layer in the multilayer laminate of the present invention can be formed into a film by a molding method of processing an unsaturated carboxylic acid grafted polyolefin with a normal polyolefin resin, and blown film molding, cast molding, extrusion lamination molding, calender molding, sheet Examples include molding, fiber molding, blow molding, injection molding, rotational molding, and coating molding. Moreover, in film forming, if necessary, it is possible to perform coextrusion molding or multilayer lamination using the polyolefin grafted with the unsaturated carboxylic acid of the present invention at least on one side.

  Multi-layer base materials include not only resin films such as polyamide, polyester, ethylene-vinyl alcohol resin, but also metal foil such as paper, aluminum foil, stainless steel foil, copper foil, aluminum plate, stainless steel plate, copper plate, glass It is also possible to laminate with different materials such as. If a thin layer is required, dissolve the polyolefin grafted with unsaturated carboxylic acid in an organic solvent, cast the solution onto a substrate such as PET, and volatilize the solvent before peeling. It is also possible to form a film by the method of, i.e., solvent casting. Furthermore, a solution obtained by dissolving the above-described polyolefin in an organic solvent is directly applied to the above-described metal foil, metal sheet, metal plate, or the like, or directly on a layer of different materials such as various resins, various glasses, and paper. A two-layered metal foil laminate, metal sheet laminate, metal plate laminate, resin film laminate, resin plate that has been provided with adhesiveness, insulation, and heat-fusibility by volatilizing the solvent after coating with a thickness A laminate, a resin sheet laminate, a glass laminate, and a paper laminate can be obtained.

  On the other hand, cast film formation using a solvent is also possible. When using the solution casting method, for example, a film in which the resin of the present invention is dissolved in a solvent such as 1,1,2-trichloroethane, chloroform or methyl ethyl ketone is cast on a polyethylene terephthalate film and the solvent is removed by volatilization. can do.

  Single layer film of unsaturated carboxylic acid grafted polyolefin, or multilayer film in which single layer sheet is laminated with other resin or other material including inorganic or metal material, multilayer sheet, multilayer extrusion lamination molded body, multilayer blow container, It is possible to produce a multilayer two-color molded body, a multilayer profile extrusion molded body, an insert injection molded body with a metal member, and the like. Specifically, food packaging films, food containers, or gasoline tanks with multilayered EVOH films or sheets as barrier layers, multilayer fibers, steel pipe coatings, stainless steel plates, colored steel plates, copper-laminated laminated films, copper wire surface adhesion Products coated with the unsaturated carboxylic acid grafted polyolefin of the present invention on the surface or inner surface of a metal material typified by an agent, copper wire coating, etc., or a multilayer in which an inner layer has a resin and their foams and the surface is a metal Intermediate adhesive layer between surface metal layer and inner resin layer in molded body, intermediate film for laminated glass used for bonding inorganic glass, intermediate film used for bonding optical film and glass, various resins and inorganic filler, nano Examples include compatibilizers, paints, and inks that have increased affinity with fillers or pigments.

  In the multilayer laminate of the present invention, the elastic electrical insulating layer can be adhered to the metal layer as a film, sheet or tape using an automated process to provide an insulating coating. For example, in a method of bonding by passing a laminating roller for bonding a film to the metal layer, the metal layer can be bonded by a method of preheating near the melting temperature of the elastic film. On the other hand, a method of thermocompression bonding with a laminator without preheating the metal layer is also possible, and there is no limitation on the laminating method as long as the elastic electrical insulating layer can be heated to a temperature at which adhesiveness is exhibited. Absent. When the metal is preheated, hot air blowing or induction heating can be used. In any case, making use of the fact that the resin of the present invention is thermoplastic makes it easy to automate the production of the laminate.

  The fusion bonding temperature of the elastic electrical insulating layer in the multilayer laminate of the present invention is 40 to 250 ° C. If the temperature is lower than 40 ° C., the elastic electrical insulating layer may not be sufficiently melted and the adhesive strength may be reduced. If the temperature exceeds 250 ° C., coloring due to thermal deterioration or the like of the elastic electrical insulating layer may be observed. In addition, the adhesive strength may be reduced due to deterioration of the elastic electrical insulating layer. Preferably it is 80-200 degreeC.

  The pressure used for fusion bonding of the elastic electrical insulating layer in the multilayer laminate of the present invention is not particularly limited as long as the electrical insulating layer is fused, but the adhesion of the adhesive interface is maintained, and the elastic electrical insulating layer In order to suppress a decrease in the thickness of the layer due to flow, the pressure is preferably 0.01 to 20 MPa, and more preferably 0.01 to 5 MPa. The pressure at the time of bonding is preferably selected according to the type of adherend.

  When the elastic electrical insulating layer in the present invention is applied to a metal layer such as tin-plated aluminum or silver flash-plated copper, an elastic electrical insulating layer firmly bonded to the metal layer is formed. By using an elastic electrical insulating layer instead of the melt-bonded epoxy powder, it is possible to bond at a temperature lower than the temperature at which a low melting point metal such as tin plating is softened. Moreover, since the obtained elastic electrical insulating layer has elasticity, it can follow a rapid change in temperature, bending of the substrate, and the like. These characteristics greatly reduce the risk of damaging the metal plating layer, and are superior in operability compared to fluidized bed coating technology.

  Unlike the conventionally used thermosetting resins that are weak against thermal shock, the multilayer laminate of the present invention is a laminate that is resistant to thermal shock and excellent in adhesiveness by using an elastic electrical insulating layer. Furthermore, in the present invention, an unsaturated carboxylic acid grafted polyolefin is used as the elastic electrical insulating layer, and the multilayer laminate is continuously and in a short time by thermocompression bonding under a relatively low temperature condition of 40 ° C. to 250 ° C. The present invention provides a laminate having a very wide application range and a method for producing the same.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited only to a following example.

<Raw material>
The following raw materials were used in the examples of the present invention.

(1) EVA
Ethylene / vinyl acetate copolymer: Ultrasen (registered trademark) 751 manufactured by Tosoh Corporation (vinyl acetate content = 28 wt%, MFR = 5.7 g / 10 min, density = 952 kg / m ³ )
(2) L-LDPE
Ethylene / hexene-1 copolymer: Nipolon-Z (registered trademark) ZF230 (MFR = 2.0 g / 10 min, density = 920 kg / m ³ ) manufactured by Tosoh Corporation
(3) PP
Homopolypropylene: Chisso Polypro XF1811 manufactured by Chisso Petrochemical Co., Ltd. (MFR = 2.5 g / 10 min, density = 900 kg / m ³ )
(4) HDPE
High density polyethylene: Nipolon Hard (registered trademark) 4000 manufactured by Tosoh Corporation (MFR = 5.0 g / 10 min, density = 965 kg / m ³ )
(5) Benzoyl peroxide (BPO)
NIPPER B made by NOF Corporation
(6) Di (2-t-butylperoxyisopropyl) benzene (DBPIB)
Perbutyl P manufactured by Nippon Oil & Fat Co., Ltd.
(7) 2,6-di-tert-butyl-p-cresol (BHT)
API Corporation Yoshinox BHT
(8) Maleic anhydride, acrylic acid, ethyl acrylate, butyl acrylate, 1,1,2-trichloroethane, xylene, methanol, dimethylformamide, BHT, 26% sulfuric acid aqueous solution, thymol blue indicator, N / 20 KOH solution Used a first grade reagent manufactured by Kanto Chemical Co., Inc.

<Adhesion test>
The following resins and metals were used for the adhesion test.

(1) Polyimide film UPILEX (registered trademark) 755 manufactured by Ube Industries, Ltd.
(2) Polycarbonate film Panlite (registered trademark) PC-2151 manufactured by Teijin Chemicals Limited
(3) Polyethylene terephthalate film Lumirror # 100 manufactured by Toray Industries, Inc.
(4) Polyphenylene sulfide (PPS)
Tosoh Co., Ltd. Sustil (registered trademark) GS40
(5) Copper plate CU-113328 0.10m made by Nilaco Corporation
(6) Aluminum plate Toyo Aluminum Co., Ltd. Count: A1N30H-H18 Thickness: 100 μm
<Acid value>
A polymer sample (1 g) is weighed and dissolved in 100 ml of toluene by heating, and then 10 ml of methanol, 10 ml of dimethylformamide and 0.5 ml of water are added. Subsequently, 1 ml of thymol blue indicator was added, titrated with an N / 20 KOH solution (n-propanol / benzene solution), and the point where the blue-violet color persisted for 1 minute or longer was calculated as the end point.

<Melt Mass Flow Rate (MFR)>
The melt mass flow rate (MFR) is JISK6922-1 for polyethylene, JISK6924-1 for ethylene vinyl acetate copolymer, and JISK6921-2 for polypropylene, respectively. The measurement was performed under the conditions of a measurement temperature of 190 ° C. and a load of 2.16 kgf.

<Measurement of gel fraction>
After 50 mg of polymer was added to 50 ml of xylene and dissolved at 140 ° C. for 12 hours, this solution was filtered through a 200 mesh stainless steel mesh (75 μm), and the unmelted portion on the wire mesh was dried at 105 ° C. for 5 hours. Calculated.

<Measurement of Yellow Index (YI)>
In accordance with JIS K7105 (1981 edition), a heating compression temperature of 150 ° C., a pressure of 10 MPa, 10 minutes, a cooling temperature of 30 ° C., a pressure of 10 MPa using a reciprocating compression molding machine WFA-50 manufactured by Shinto Metal Industries, Ltd. YI of a film having a thickness of 100 μm pressed under conditions of 5 minutes was measured using an SM color computer manufactured by Suga Test Instruments Co., Ltd.

<Amount of 1-butanol and 1,2-epoxybutane in 1,1,2-trichloroethane>
A gas chromatograph apparatus (0.5 μl of 1,1,2-trichloroethane was collected by a microsyringe and attached with a GC capillary column DB-1301 (Agilent Technologies, Inc., length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm)) Shimadzu Corporation GC-14A) was measured under the following conditions.

Injection temperature: 40 ° C
Injection temperature holding time: 4 minutes Temperature rising program 1: 5 ° C / minute (40 ° C to 90 ° C)
Temperature rising program 2: 10 ° C./min (90 ° C. to 190 ° C.)
Final temperature: 190 ° C
Final temperature holding time: 20 minutes Carrier gas: Helium <Adhesion test>
By using a reciprocating compression molding machine WFA-50 manufactured by Shindo Metal Industry Co., Ltd. as a press molding machine, under the press conditions of heating temperature 150 ° C., pressure 10 MPa, 10 minutes, cooling temperature 30 ° C., pressure 10 MPa, 5 minutes. A press film having a thickness of 100 μm was obtained. The film and adherend molded to a thickness of 100 μm were thermocompression bonded using a heat seal tester TP-701 manufactured by Tester Sangyo Co., Ltd. under the conditions of 180 ° C., 60 seconds, and 0.2 MPa. The adhesive strength was evaluated by a T-type peel test using a Tensilon universal tester RTE-1210 (Orientec Co., Ltd.) as a tensile tester under the condition of a tensile speed (peeling speed) of 300 mm / min.

<Melting extrusion>
A 10-zone twin-screw extruder (115 mmφ, L / D = 50) manufactured by Nakatani Machinery Industry with a vent was used.

<Heat cycle test>
Using a thermal shock device TSA-71L-A manufactured by ESPEC CORP., Heat shock was applied to the adhesion test piece for 30 minutes at 85 ° C., 5 minutes at room temperature, and 30 minutes at −40 ° C., and the adhesion piece was peeled off. Etc. were observed.

Example 1
<Production of unsaturated carboxylic acid grafted polyolefin>
5000 parts by weight of 1,1,2-trichloroethane and 2500 parts by weight of a 26% sulfuric acid aqueous solution were placed in a 10-liter flask with a lower mouth and stirred vigorously. After standing at rest, the lower organic layer was extracted. Next, 5 kg of the extracted organic layer and distilled water was placed in a 10-liter flask with a lower mouth and stirred vigorously, and after standing, the operation of extracting the lower organic layer was repeated three times to remove impurities 1-butanol and 1,2 -Excluding epoxy butane. Further, 150 parts by weight of molecular sieves 4A was added to the extracted organic layer, dehydrated by stirring with a stirrer, and purified 1,1,2-trichloroethane (hereinafter referred to as purified TCE).

  A 4 liter glass reaction vessel was charged with purified TCE, 2480 parts by weight, 200 parts by weight of EVA, and 4.1 parts by weight of maleic anhydride. The temperature of the reactor was raised to 80 ° C., and then maintained at 80 ° C. for 4 hours to uniformly dissolve EVA. During this time, nitrogen gas was introduced into the reactor at a flow rate of 5 liters / minute to eliminate air mixed in the reactor. As a catalyst for the graft reaction, 1.5 parts by weight of BPO was dissolved in 100 parts by weight of purified TCE. While continuously adding this solution to the reactor, the graft reaction was carried out for 3 hours while maintaining the pressure of the reactor at 1 MPa. After completion of the reaction, the pressure was returned to normal pressure, the temperature of the reactor was lowered to 70 ° C., and 0.06 part by weight of BHT was added as a stabilizer. This solution was poured into a large amount of methanol, and the product maleic anhydride grafted EVA was separated from the solvent.

  The product was analyzed and found to have 1.5% by weight of unsaturated carboxylic acid (maleic anhydride). The gel was 0% by weight, YI was 2, and the hue was good.

<Production of unsaturated carboxylic acid grafted polyolefin film>
The unsaturated carboxylic acid graft EVA obtained as described above was subjected to heating temperature 150 ° C., pressure 10 MPa, heating time 10 minutes, cooling temperature 30 ° C., pressure 10 MPa, cooling time 5 using a reverse compression molding machine WFA-50. A film (film 1) having a size of 50 mm × 100 mm and a thickness of 100 μm was obtained by press molding under the condition of minutes. The appearance and properties of the obtained film were good, and no defects such as fish eyes were observed.

<Copper sheet insulation coating>
The obtained film having a size of 50 mm × 100 mm and a thickness of 100 μm (film 1), an untreated surface of size 100 mm × 100 mm, a thickness of 0.5 mm copper sheet (sheet 1), a size of 100 mm × 100 mm and a thickness of 100 μm of polyimide film ( A laminate in which film 2) is laminated in the configuration of sheet 1 / film 1 / film 2 and a copper sheet and a half area of polyimide film are bonded under the conditions of pressure 0.2 Mpa, temperature 180 ° C., time 1 minute. Obtained. A strip sample having a length of 100 mm and a width of 15 mm was cut from the obtained laminate so that half of the area was adhered and half of the area was not adhered, and the tension rate was 300 mm / min. When a T-type peel test was performed, the laminate showed an excellent peel strength of 40 N / 15 mm. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

実施例２
実施例１と同様の手法でアクリル酸をグラフトしたＥＶＡを製造し、フィルム化した後接着試験を行った。被着体を銅シート、及び、アルミニウムシートとした以外は実施例１と同様の手法により積層体を得た。この積層体の剥離試験を実施した結果、本積層体は３８Ｎ／１５ｍｍの非常に強い剥離強度を示した。また、本試験片は２００回のヒートサイクル試験で、積層体を構成する各材料間で剥離、破壊を生じず、熱衝撃に強い積層体であることが確認できた。その結果を表１に示す。

Example 2
An EVA grafted with acrylic acid was produced in the same manner as in Example 1, formed into a film, and then subjected to an adhesion test. A laminate was obtained in the same manner as in Example 1 except that the adherend was a copper sheet and an aluminum sheet. As a result of carrying out a peel test of this laminate, this laminate showed a very strong peel strength of 38 N / 15 mm. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 3
EVA grafted with maleic anhydride and butyl acrylate was produced in the same manner as in Example 1, and after film formation, an adhesion test was conducted. 5-layer laminate consisting of copper sheet / EVA film grafted with maleic anhydride and butyl acrylate / polycarbonate film / EVA film grafted with maleic anhydride and butyl acrylate / copper sheet in the same manner as in Example 1. Got. As a result of carrying out the peel test of this laminate, this laminate has a very strong peel strength with a peel strength between layer 1 / layer 3 of 42 N / 15 mm and a peel strength between layer 3 / layer 5 of 36 N / 15 mm. Indicated. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 4
EVA grafted with maleic anhydride and ethyl acrylate was prepared in the same manner as in Example 1, and after film formation, an adhesion test was conducted. 5 layer laminate comprising aluminum sheet / EVA film grafted with maleic anhydride and ethyl acrylate / PPS sheet / EVA film grafted with maleic anhydride and ethyl acrylate / copper sheet by the same method as in Example 1. Got. As a result of carrying out the peel test of this laminate, this laminate has a very strong peel strength of 50 N / 15 mm between layers 1 and 3 and 41 N / 15 mm between layers 3 and 5. Indicated. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 5
An EVA grafted with acrylic acid was produced in the same manner as in Example 1, formed into a film, and then subjected to an adhesion test. A laminate was obtained in the same manner as in Example 1 except that Example 1 and the adherend were made of an aluminum sheet having a thickness of 0.5 mm and a polyimide film having a thickness of 100 μm. As a result of carrying out a peel test of this laminate, the laminate showed a very strong peel strength of 51 N / 15 mm. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 6
EVA grafted with maleic anhydride was produced in the same manner as in Example 1 and formed into a film, and then an adhesion test was conducted. A laminate was obtained in the same manner as in Example 1 except that Example 1 and the adherend were made of an aluminum sheet having a thickness of 0.5 mm and a polycarbonate film having a thickness of 100 μm. As a result of the peel test of this laminate, this laminate showed a very strong peel strength of 53 N / 15 mm. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 7
EVA grafted with maleic anhydride was produced in the same manner as in Example 1 and formed into a film, and then an adhesion test was conducted. A laminate was obtained in the same manner as in Example 1 except that Example 1 and the adherend were made of an aluminum sheet having a thickness of 0.5 mm and PPS having a thickness of 1 mm. As a result of carrying out a peel test of this laminate, this laminate showed a very strong peel strength of 55 N / 15 mm. In addition, the test piece was confirmed to be a laminate that was resistant to thermal shock without peeling or breaking between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 1.

Example 8
An LDPE grafted with maleic anhydride was produced in the same manner as in Example 1 except that the polyolefin was changed to LDPE, and the film was made into a film and subjected to an adhesion test. The results are shown in Table 1.

Example 9
An HDPE grafted with maleic anhydride was produced in the same manner as in Example 1 except that the polyolefin was changed to HDPE, and the film was made into a film and subjected to an adhesion test. The results are shown in Table 2.

実施例１０
ポリオレフィンをＬ−ＬＤＰＥに変えた以外は実施例１と同様の手法により無水マレイン酸及びアクリル酸をグラフトしたＬ−ＬＤＰＥを製造し、フィルム化して接着試験を行った。実施例１と同様の手法により、銅シート／無水マレイン酸及びアクリル酸をグラフトしたＬ−ＬＤＰＥフィルム／ポリカーボネートフィルム／無水マレイン酸及びアクリル酸をグラフトしたＬ−ＬＤＰＥフィルムからなる４層の積層体を得て、この積層体の剥離試験を実施した。その結果を表２に示す。

Example 10
An L-LDPE grafted with maleic anhydride and acrylic acid was produced in the same manner as in Example 1 except that the polyolefin was changed to L-LDPE, and a film was formed to perform an adhesion test. In the same manner as in Example 1, a four-layer laminate comprising a copper sheet / an L-LDPE film grafted with maleic anhydride and acrylic acid / a polycarbonate film / an L-LDPE film grafted with maleic anhydride and acrylic acid. Obtained and a peel test of this laminate was carried out. The results are shown in Table 2.

Example 11
A 10 L separable flask equipped with a stirrer, UV irradiation device, and reflux condenser is charged with 500 parts by weight of MFR 2.5, 900 kg / m ³ density polypropylene, 8 L of ion-exchanged water, and 0.23 parts by weight of sodium alkyl sulfonate. A suspension was prepared. While irradiating this suspension with UV, chlorine gas was continuously introduced and reacted at 100 ° C. for 6 hours to obtain a chlorinated polypropylene having a chlorine content of 20%.

  Using the obtained chlorinated PP, a CPP grafted with maleic anhydride was obtained in the same manner as in Example 1, and then formed into a film and subjected to an adhesion test. In the same manner as in Example 1, a five-layer laminate comprising a copper sheet / maleic anhydride grafted CPP film / polyimide film / maleic anhydride grafted CPP film / copper sheet was obtained. A peel test was performed. The results are shown in Table 2.

Example 12
L-LDPE grafted with maleic anhydride and butyl acrylate was produced in the same manner as in Example 1 except that the L-LDPE was changed to MFR2 and density 920 kg / m ³ . Further, the obtained modified L-LDPE was formed into a film by the same method as in Example 1, and an adhesion test was performed. 5 consisting of an aluminum sheet / L-LDPE film grafted with maleic anhydride and butyl acrylate / polyimide film / L-LDPE film grafted with maleic anhydride and butyl acrylate / aluminum sheet in the same manner as in Example 1. A laminate of layers was obtained and a peel test of this laminate was performed. The results are shown in Table 2.

Example 13
A PP grafted with maleic anhydride was produced in the same manner as in Example 1 except that the polyolefin was changed to PP, and a film was formed to conduct an adhesion test. In the same manner as in Example 1, a four-layer laminate consisting of a copper sheet / PP film grafted with maleic anhydride / polyimide film / PP film grafted with maleic anhydride was obtained, and the peel test of this laminate was conducted. Carried out. The results are shown in Table 2.

Example 14
An EVA grafted with acrylic acid was produced in the same manner as in Example 1, and an EVA film grafted with acrylic acid was bonded to one side of an aluminum sheet having a thickness of 0.5 mm. Under the present circumstances, the laminated body was obtained by the method similar to Example 1 using the film of acrylic acid graft EVA which protected the surface on the opposite side to the surface which adhere | attaches an aluminum sheet with the polyethylene terephthalate film. As a result of carrying out the peel test of this laminate, the EVA film was first broken because the adhesive strength between the EVA film and the aluminum sheet was strong. In addition, it was confirmed that the test piece was a laminate that was resistant to thermal shock without peeling between the materials constituting the laminate in 200 heat cycle tests. The results are shown in Table 2.

Example 15
An aluminum sheet / maleic anhydride graft EVA film / copper sheet / anhydrous comprising an aluminum sheet having a thickness of 0.5 mm, a copper sheet having a thickness of 0.5 mm, and a maleic anhydride graft EVA film having a thickness of 100 μm in the same manner as in Example 1. A four-layer laminate composed of a maleic acid graft EVA film was obtained. Table 2 shows the results of the adhesion test of this laminate.

Comparative Example 1
Using Nakamachi's 115 machine industry mmφ, L / D = 50 twin screw extruder, set zones C1, C2, and C3 to 150, 180, and 200 ° C, and zones C4 to C10, A, and D to 220 ° C. Then, the unreacted unsaturated carboxylic acid was removed from the vent between C6 and C7 at a rotation speed of 110 rpm, and a graft reaction was performed. That is, a pre-blend that was uniformly mixed using a Henschel mixer at a ratio of 100 parts by weight of EVA, 4 parts by weight of maleic anhydride, 2 parts by weight of BPO was supplied to a twin-screw extruder and grafted to maleic anhydride. EVA was obtained. As a result of analysis, the obtained EVA was confirmed to contain 0.6% by weight maleic anhydride and 0.15% by weight gel.

<Production of unsaturated carboxylic acid grafted polyolefin film>
Using a compression compression molding machine WFA-50, the obtained maleic anhydride graft EVA was heated at 150 ° C., pressure 10 MPa, heating time 10 minutes, cooling temperature 30 ° C., pressure 10 MPa, cooling time 5 minutes. A film having a thickness of 100 μm was obtained by press molding. The obtained film had fish eyes and the appearance was clearly inferior to the films obtained in the examples.

  The obtained film having a size of 50 mm × 100 mm and a thickness of 100 μm (film 3), an untreated surface of size 100 mm × 100 mm, a thickness of 0.5 mm copper sheet (sheet 1), a size of 100 mm × 100 mm and a thickness of 100 μm of polyimide film ( A laminate in which film 2) is laminated in a configuration of sheet 1 / film 3 / film 2, and the foil 1 and half the area of the polyimide film are bonded under the conditions of pressure 0.2 MPa, temperature 180 ° C., and time 1 minute. Obtained. A strip-shaped sample having a length of 100 mm and a width of 15 mm was cut out from the obtained laminate so that half of the area was adhered and half of the area was not adhered, and the tensile speed was 300 mm / min. When a T-type peel test was performed, the laminate had a low peel strength of 13 N / 15 mm. Moreover, this test piece produced the peeling between each material which comprises a laminated body in 20 heat cycle tests, and was a laminated body weak to a thermal shock compared with the laminated body obtained in the Example. The results are shown in Table 3.

比較例２
比較例１と同様の手法で無水マレイン酸及びアクリル酸をグラフトしたＥＶＡを製造し、比較例１の被着体を銅シート、及び、アルミニウムシートとした以外は実施例１と同様の手法により積層体を得た。この積層体の剥離試験を実施した結果、本積層体は１５Ｎ／１５ｍｍと低い剥離強度を示した。また、本試験片は５０回のヒートサイクル試験で、積層体を構成する各材料間で剥離を生じ、実施例で得られた積層体に比べ熱衝撃に弱い積層体であった。その結果を表３に示す。

Comparative Example 2
A EVA grafted with maleic anhydride and acrylic acid was produced in the same manner as in Comparative Example 1 and laminated in the same manner as in Example 1 except that the adherend of Comparative Example 1 was a copper sheet and an aluminum sheet. Got the body. As a result of carrying out a peel test of this laminate, this laminate showed a low peel strength of 15 N / 15 mm. In addition, the test piece was a laminate that was susceptible to thermal shock as compared with the laminate obtained in the Examples, as a result of peeling between the materials constituting the laminate in 50 heat cycle tests. The results are shown in Table 3.

Comparative Example 3
EVA grafted with maleic anhydride and butyl acrylate was produced in the same manner as in Comparative Example 1, and the adherend of Comparative Example 1 was made of a copper sheet (Layer 1), a polycarbonate film (Layer 3), and a copper sheet (Layer 5). The layered product was obtained in the same manner as in Example 1 except that the structure was changed. As a result of carrying out a peel test of this laminate, this laminate showed a low value of 10 N / 15 mm between the layers 1 and 3 and 12 N / 15 mm between the layers 3 and 5. Further, this test piece was a laminate that was susceptible to thermal shock as compared with the laminate obtained in the Examples, as a result of peeling between the materials constituting the laminate in 18 heat cycle tests. The results are shown in Table 3.

Comparative Example 4
EVA produced by grafting maleic anhydride in the same manner as in Comparative Example 1, except that the adherend of Comparative Example 1 was an aluminum sheet (Layer 1), a PPS sheet (Layer 2), and a copper sheet (Layer 3) Obtained a 5-layer laminate by the same method as in Example 1. As a result of carrying out the peel test of this laminate, this laminate showed a low value of 10 N / 15 mm peel strength between layer 1 / layer 3 and 11 N / 15 mm peel strength between layer 3 / layer 5. In addition, this test piece was a laminate that was susceptible to thermal shock as compared with the laminate obtained in the Examples, as a result of peeling between the materials constituting the laminate in 35 heat cycle tests. The results are shown in Table 3.

Comparative Example 5
A EVA grafted with maleic anhydride was produced in the same manner as in Comparative Example 1 and shown in Table 3 by the same procedure as in Example 1 except that the adherend of Comparative Example 1 was an aluminum sheet and a polyimide film. A four-layer laminate was obtained. As a result of carrying out the peel test of this laminate, this laminate showed a low peel strength between layer 1 / layer 3 as low as 9 N / 15 mm and a low peel strength between layer 3 / layer 4 as 7 N / 15 mm. . In addition, the test piece was a laminate that was susceptible to thermal shock as compared with the laminates obtained in the examples as a result of peeling between the materials constituting the laminate in 30 heat cycle tests. The results are shown in Table 3.

Comparative Example 6
A EVA grafted with maleic anhydride was produced in the same manner as in Comparative Example 1, and Table 3 shows the same procedure as in Example 1 except that the adherend of Comparative Example 1 was an aluminum sheet and polycarbonate. A four-layer laminate was obtained. As a result of carrying out a peel test of this laminate, this laminate showed a low peel strength between layers 1 and 3 of 11 N / 15 mm and a low peel strength between layers 3 and 4 of 8 N / 15 mm. . In addition, the test piece was a laminate that was susceptible to thermal shock as compared with the laminate obtained in the examples, as a result of peeling between the materials constituting the laminate in 32 heat cycle tests. The results are shown in Table 3.

Comparative Example 7
A EVA grafted with maleic anhydride was produced in the same manner as in Comparative Example 1, and the results are shown in Table 3 in the same manner as in Example 1 except that the adherend of Comparative Example 1 was an aluminum sheet and PPS. A four-layer laminate was obtained. As a result of carrying out a peel test of this laminate, this laminate showed a low peel strength between layers 1 and 3 of 8 N / 15 mm and a low peel strength between layers 3 and 4 of 7 N / 15 mm. Further, this test piece was a laminate that was susceptible to thermal shock compared to the laminates obtained in the Examples, as a result of peeling between the materials constituting the laminate in 26 heat cycle tests. The results are shown in Table 3.

Comparative Example 8
A CPP grafted with maleic anhydride was produced in the same manner as in Comparative Example 1 using the CPP obtained in Example 11, and the resulting polymer was formed into a film, and then a copper sheet / maleic anhydride grafted CPP. Table 3 shows the results of manufacturing a laminate of 4 layers of film / polyimide film / maleic anhydride grafted CPP film and performing an adhesion test thereof. As a result of the adhesion test, the laminate was inferior to the laminate obtained in the examples in all of the physical properties of adhesive strength, hue, and thermal shock. The results are shown in Table 3.

Claims (4)

A multilayer laminate comprising at least one of a metal layer and a resin layer and an elastic electrical insulation layer, wherein the metal layer and / or the resin layer and the elastic electrical insulation layer are bonded, the elastic electrical insulation layer comprising: A multilayer laminate comprising a modified polyolefin grafted with an unsaturated carboxylic acid, wherein the modified polyolefin grafted with the unsaturated carboxylic acid does not contain a gel insoluble in xylene heated to 140 ° C. The multilayer laminate according to claim 1, wherein the metal layer and / or the resin layer and the elastic electrical insulating layer are bonded by thermocompression bonding. The multilayer laminate according to claim 1 or 2, further comprising 20 to 40 parts by weight of a flame retardant with respect to 100 parts by weight of the modified polyolefin grafted with an unsaturated carboxylic acid. 4. The method according to any one of claims 1 to 3, wherein the metal layer and the elastic electrical insulating layer are superposed and pressure bonded under pressure and at a temperature of 40 ° C to 250 ° C. A method for producing a multilayer laminate.