WO2014054409A1 - 多層熱回復物品 - Google Patents

多層熱回復物品 Download PDF

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Publication number
WO2014054409A1
WO2014054409A1 PCT/JP2013/074954 JP2013074954W WO2014054409A1 WO 2014054409 A1 WO2014054409 A1 WO 2014054409A1 JP 2013074954 W JP2013074954 W JP 2013074954W WO 2014054409 A1 WO2014054409 A1 WO 2014054409A1
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WIPO (PCT)
Prior art keywords
adhesive composition
heat recovery
recovery article
adhesive layer
adhesive
Prior art date
Application number
PCT/JP2013/074954
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English (en)
French (fr)
Inventor
智 山崎
西川　信也
安隆 江本
竜平 藤田
Original Assignee
住友電気工業株式会社
住友電工ファインポリマー株式会社
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Publication date
Application filed by 住友電気工業株式会社, 住友電工ファインポリマー株式会社 filed Critical 住友電気工業株式会社
Priority to CN201380004126.XA priority Critical patent/CN103974828B/zh
Priority to EP13844472.4A priority patent/EP2905132B1/en
Priority to US14/365,644 priority patent/US20150004408A1/en
Publication of WO2014054409A1 publication Critical patent/WO2014054409A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
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    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
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    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J131/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Adhesives based on derivatives of such polymers
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    • C09J131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
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    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/303—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups H01B3/38 or H01B3/302
    • H01B3/305—Polyamides or polyesteramides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/448—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from other vinyl compounds
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    • B32B2250/24—All layers being polymeric
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/04—Presence of homo or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C09J2423/04—Presence of homo or copolymers of ethene
    • C09J2423/046—Presence of homo or copolymers of ethene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2427/00—Presence of halogenated polymer
    • C09J2427/006—Presence of halogenated polymer in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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Definitions

  • the present invention relates to a multilayer heat recovery article having an adhesive layer on the inner surface.
  • Heat-shrinkable tubes such as heat-shrinkable tubes and heat-shrinkable caps that are heat-shrinkable in the radial direction are used for insulation wire connection and terminal treatment of various equipment wiring, metal tube waterproofing, corrosion protection, etc.
  • Heat-shrinkable tubes such as heat-shrinkable tubes and heat-shrinkable caps that are heat-shrinkable in the radial direction are used for insulation wire connection and terminal treatment of various equipment wiring, metal tube waterproofing, corrosion protection, etc.
  • a heat-shrinkable tube is covered with a connection portion of an insulated wire and heated, the heat-shrinkable tube shrinks and adheres along the shape of the connection portion, so that it can be protected from injury and the like.
  • a heat-shrinkable tube with an adhesive having an adhesive layer provided on the inner surface is used.
  • Patent Document 1 describes a heat recovery article having an adhesive composition layer formed on the inner surface.
  • a hot melt adhesive such as an ethylene-vinyl acetate copolymer (EVA), an ethylene-ethyl acrylate copolymer (EEA), or a polyamide resin is used.
  • a heat-shrinkable tube having an adhesive layer is formed by extruding an outer layer and an inner layer (adhesive layer) in a tube shape, then expanding (expanding diameter) in the radial direction under heating, and cooling to fix its shape. It is manufactured by.
  • the outer layer material may be crosslinked by crosslinking ionizing radiation after extrusion.
  • coat the heat-shrinkable tube on the outside of the substrate to be treated and then heat it to heat-shrink the outside.
  • the inner adhesive layer is flowed to fill the space between the substrate to be treated and the outer layer.
  • Patent Document 2 describes a heat-shrinkable tube in which an adhesive layer has two thermoplastic resin layers.
  • the adhesive layer used for the inner layer of the heat recovery article is required to have high fluidity because it is necessary to easily adhere to the adherend to ensure the filling property during heat shrinkage.
  • the fluidity is too high, the shape of the adhesive layer is not stable when extruding the heat-recovery article, and the thickness variation of the adhesive layer increases.
  • the inner diameter of the adhesive layer is small, the cavity inside the adhesive layer is filled, and it may be difficult to expand the diameter.
  • the present invention has been made in view of the above-mentioned problems, and it is possible to secure adhesiveness with a substrate to be processed by improving the embedding property at the time of heat shrinkage and to reduce the thickness variation of the adhesive layer at the time of extrusion molding. It is an object to provide a heat recovery article.
  • the present invention includes a thermoplastic resin having a melt flow rate of 15 g / 10 min to 1000 g / 10 min at a temperature of 190 ° C. and a load of 2.16 kg, and an organically treated layered silicate, a temperature of 150 ° C., and a shear rate.
  • a multilayer heat recovery article having an adhesive layer made of an adhesive composition having a shear viscosity at 0.1 s ⁇ 1 of 1000 Pa ⁇ s or more and an outer layer on the outer periphery of the adhesive layer.
  • an adhesive layer having good fluidity By containing a thermoplastic resin having a melt flow rate of 15 g / 10 min to 1000 g / 10 min at a temperature of 190 ° C. and a load of 2.16 kg in the adhesive composition, an adhesive layer having good fluidity can be obtained.
  • the adhesion to the substrate to be treated during heat shrinkage is improved.
  • the adhesive composition contains an organically treated layered silicate, and the fluidity of the adhesive layer during extrusion molding is increased by setting the shear viscosity at a temperature of 150 ° C. and a shear rate of 0.1 s ⁇ 1 to 1000 Pa ⁇ s or more.
  • the thickness variation of the adhesive layer can be reduced.
  • a heat-recovery article that can improve the filling property at the time of heat shrinkage and improve the adhesion to the substrate to be treated, and can reduce the thickness variation of the adhesive layer at the time of extrusion molding.
  • FIG. 1 is a schematic sectional view showing an example of the heat recovery article of the present invention.
  • An outer layer 2 is provided on the outer periphery of the tubular adhesive layer 1.
  • the adhesive layer 1 is made of an adhesive composition having a thermoplastic resin having a melt flow rate of 15 g / 10 min to 1000 g / 10 min at a temperature of 190 ° C. and a load of 2.16 kg, and an organically treated layered silicate. .
  • Melt flow rate is an index that represents the fluidity of the resin, and is measured under the conditions of a temperature of 190 ° C. and a load of 2.16 kg in accordance with JIS K7210 using an extrusion plastometer defined in JIS K6760. is there.
  • the thermoplastic resin used in the adhesive composition any resin can be used as long as it has an MFR of 15 g / 10 min or more and 1000 g / 10 min or less.
  • EVA ethylene-vinyl acetate copolymer
  • ESA ethylene-ethyl acrylate copolymer
  • saturated copolymer polyester etc.
  • thermoplastic resin having an MFR of more than 1000 g / 10 minutes is too fluid to be stably extruded. Moreover, the fluidity
  • the MFR of the thermoplastic resin is more preferably 100 g / 10 min or more and 800 g / 10 min or less.
  • ethylene-vinyl acetate copolymer and polyamide can be particularly preferably used because of excellent dispersibility of the organically treated layered silicate.
  • An ethylene-vinyl acetate copolymer and polyamide may be used alone, or both may be mixed.
  • the ethylene-vinyl acetate copolymer those having a vinyl acetate content of 12 mass% to 46 mass% are particularly preferred. If vinyl acetate content is 12 mass% or more, dispersion
  • the organically treated layered silicate is obtained by organically treating layered silicates (clay mineral, clay) such as montmorillonite, bentonite and smectite. Between the layered silicate planes, intermediate layer cations such as magnesium ions, sodium ions, and calcium ions are present to maintain a layered crystal structure. This intermediate layer cation is ion-exchanged with the organic cation by organic treatment.
  • the organic compound is chemically bonded to the surface of the silicate plane and introduced between layers (intercalation), thereby increasing the interlayer distance between the silicate planes and improving the dispersibility in the thermoplastic resin.
  • layered silicate either a natural product or a synthetic product can be used.
  • An organically treated layered silicate is dispersed in a thermoplastic resin to adjust the viscosity of the adhesive composition.
  • the shear viscosity at a temperature of 150 ° C. and a shear rate of 0.1 s ⁇ 1 is 1000 Pa ⁇ s or more.
  • the viscosity is a value measured with a rotary rheometer.
  • the adhesive composition When passing through a die during extrusion molding, the adhesive composition is subjected to high shear stress and has high fluidity. However, after passing through the die, the shear stress applied to the adhesive composition is reduced. If the viscosity of the adhesive composition in this state is low, the adhesive layer is deformed after passing through the die, resulting in variation in thickness or filling of the internal cavity. However, when the shear viscosity at a temperature of 150 ° C. and a shear rate of 0.1 s ⁇ 1 is 1000 Pa ⁇ s or more, the viscosity of the adhesive composition increases immediately after passing through the die, so that the flow of the adhesive layer after passing through the die is increased. The thickness variation can be reduced.
  • the shear viscosity at a temperature of 150 ° C. and a shear rate of 100 s ⁇ 1 of the adhesive composition is preferably 200 Pa ⁇ s or less.
  • the viscosity in the low shear rate region is increased as described above, the extrudability is improved.
  • the viscosity in the high shear rate region is still high, the fluidity at the time of heat shrinkage is lowered and good adhesion is achieved. It is because it cannot be obtained.
  • the heat loss at 300 ° C. of the adhesive composition is preferably 1% or more.
  • the adhesive composition includes an organically treated layered silicate. When this organically treated layered silicate is heated to 300 ° C., the organic compound contained in the organically treated layered silicate decomposes and loses weight. Therefore, the heat loss at 300 ° C. is a measure of the amount of organic compound contained in the organically treated layered silicate. It becomes.
  • the amount of the organic compound contained in the organically treated silicate is preferably 20% to 60%.
  • the organically treated layered silicate having a small organic compound content has a low dispersibility in the thermoplastic resin, and it is difficult to finely disperse the layered silicate.
  • the heat loss at 300 ° C. is a value obtained by measuring the mass loss at 300 ° C. based on the mass at 50 ° C., measured by increasing the temperature at 10 ° C./min up to 400 ° C. with a thermal analyzer.
  • the organically treated layered silicate is contained in the adhesive composition.
  • the organically treated layered silicate contains silicon (Si) and magnesium (Mg)
  • the presence of the organically treated layered silicate can also be confirmed by elemental analysis of the adhesive composition to confirm the presence of Si and Mg. can do.
  • the storage elastic modulus at 110 ° C. of the adhesive composition is preferably 0.1 MPa or less.
  • the storage elastic modulus is measured by changing the strain from 0.001% to 10% in the vibration measurement of the rotary rheometer, and is taken as the value of the storage elastic modulus at the time of 0.1% strain.
  • the storage elastic modulus is higher than 0.1 MPa, the shape is maintained even when stress is applied, so that the filling property of the adhesive layer when the outer layer contracts deteriorates.
  • the pressure is 0.1 MPa or less, the adhesive layer is easily melted when the outer layer contracts, so that the filling property when the outer layer contracts is good.
  • the content of the organically treated layered silicate is arbitrarily adjusted so that the shear viscosity at a temperature of 150 ° C. and a shear rate of 0.1 s ⁇ 1 is 1000 Pa ⁇ s or more.
  • the organically treated layered silicate is contained in an amount of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the thermoplastic resin, the viscosity can be adjusted well, which is preferable.
  • the good dispersion of the organically treated layered silicate in the thermoplastic resin can be determined using the light transmittance at a wavelength of 850 nm as an index. If the transmittance of light having a wavelength of 850 nm at a converted thickness of 1.0 mm is 30% or more, the organically treated layered silicate is presumably finely dispersed. In addition, when the layered silicate which is not organically processed is used, since the dispersibility is not good, it is estimated that the transmittance
  • the transmittance of light with a wavelength of 850 nm at a converted thickness of 1.0 mm does not exceed 30%. However, if the converted thickness is 0.05 mm, the transmittance of light having a wavelength of 850 nm is 20% or more.
  • additives other than the above thermoplastic resin and organically treated layered silicate may be mixed.
  • antioxidants, colorants, lubricants, heat stabilizers, ultraviolet absorbers and the like are used as additives.
  • These materials are mixed by an arbitrary mixer such as an open roll, a pressure kneader, a single-screw mixer, a twin-screw mixer, etc. to prepare an adhesive composition.
  • the resin composition constituting the outer layer includes one or more selected from the group consisting of polyethylene, polyester, polyamide and fluororesin as a resin component, and flame retardants, antioxidants, colorants, lubricants, thermal stability as necessary. Agents, UV absorbers, etc. are mixed.
  • the resin composition constituting the outer layer and the adhesive composition constituting the adhesive layer can be extruded using a known melt extrusion molding machine to obtain a multilayer extruded product.
  • the multilayer extruded product is expanded to a predetermined outer shape by a method such as introducing compressed air into the tube while being heated to a temperature equal to or higher than the melting point, and then cooled to fix the shape to obtain a multilayer heat recovery article.
  • a multilayer heat recovery article having excellent heat resistance is obtained.
  • a crosslinking method methods such as crosslinking by irradiation with ionizing radiation, chemical crosslinking, and thermal crosslinking can be used.
  • the shape of the multilayer heat recovery article can be designed arbitrarily.
  • the inner diameter of the outer layer is 1.0 mm to 30 mm
  • the thickness of the outer layer is 0.1 mm to 10 mm
  • the thickness of the adhesive layer is about 0.1 mm to 10 mm
  • the inner diameter of the adhesive layer is 0.00.
  • it is about 1 mm to 8.5 mm.
  • the multilayer heat-recovery article of the present invention is excellent in the extrudability of the adhesive layer, it can be satisfactorily extruded even when the inner diameter of the adhesive layer is as small as 1.0 mm or less.
  • the multilayer heat recovery article of the present invention includes a heat shrink tube and a heat shrink cap.
  • the heat-shrinkable tube is tube-shaped and may be long or cut to an appropriate length.
  • a heat-shrink cap is one in which one end of a heat-shrink tube cut to an appropriate length is closed by heating and shrinking.
  • Adhesive compositions were prepared by melting and mixing the thermoplastic resins, fillers, and antioxidants of the formulation shown in Tables 1 and 2.
  • the obtained adhesive composition was used as an inner layer (adhesive layer), polyethylene having a melting point of 125 ° C. as an outer layer, outer layer inner diameter 2.8 mm, outer layer thickness 0.9 mm, inner layer (adhesive layer) inner diameter 0.6 mm, inner layer (adhesion) Agent layer)
  • a tube-shaped two-layer extruded product having a thickness of 1.0 mm was prepared.
  • the extruded product was irradiated with ionizing radiation to crosslink the outer layer, then expanded so that the outer diameter of the outer layer was 7.5 mm, cooled, and fixed in shape to obtain a heat-shrinkable tube.
  • the adhesive layer contains an amount of antioxidant that does not crosslink, so that crosslinking is inhibited.
  • the outer layer was peeled from the heat-shrinkable tube to make only the inner layer (adhesive layer), and the following series of evaluations were performed.
  • Shear viscosity measurement The shear viscosity at a temperature of 150 ° C. was measured using a rotary rheometer (RCM302 manufactured by Anton Paar Co., Ltd.). The shear viscosity was 1 when the shear rate was 0.1 s ⁇ 1 , and the shear viscosity 2 when the shear rate was 100 s ⁇ 1 .
  • the adhesive composition was pressed at a temperature of 150 ° C. to prepare a sheet having a thickness of 1.0 mm, and the transmittance of light having a wavelength of 850 nm was measured using a spectrophotometer. Since the adhesive compositions of Example 10 and Comparative Example 8 contained carbon black and were black, a 0.05 mm thick sheet was prepared and measured in the same manner.
  • Elemental analysis of the adhesive composition was performed by energy dispersive X-ray spectroscopy. Among them, Mg, Si, and Ca were detected. The above results are shown in Tables 1 and 2.
  • EVA1 MFR 150 g / 10 min, ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by mass
  • EVA2 MFR 800 g / 10 min, ethylene-vinyl acetate copolymer having a vinyl acetate content of 28% by mass
  • EVA3 MFR 150 g / 10 min
  • EVA4 MFR 2 g / 10 min, ethylene-vinyl acetate copolymer with 5% by mass of vinyl acetate
  • Polyethylene MFR 145 g / 10 min, density 0.915
  • Organically treated layered silicate 1 Layered silicate treated with dimethyldistearylammonium chloride
  • Organically treated layered silicate 2 Layered silicate treated with benzyldimethylstearylammonium chloride
  • Organically treated swelling mica Syn
  • Wollastonite manufactured by Kinsei Matec Corporation, SH1800 Talc: MICRO ACE SG95 manufactured by Nippon Talc Co., Ltd.
  • Carbon black carbon black having an arithmetic average particle size of 24 nm, a nitrogen adsorption specific surface area of 93 m 2 / g, and a bulk density of 360 kg / m 3
  • the adhesive compositions of Examples 1 to 10 are excellent in extrusion moldability and pass the waterproof test. These adhesive compositions contain 1% by mass or more and 20% by mass or less of organically treated layered silicate with respect to 100 parts by mass of the resin.
  • the shear viscosity of the adhesive composition when the shear rate is 0.1 s ⁇ 1 is 1000 Pa ⁇ s or more, and the shear viscosity when the shear rate is 100 s ⁇ 1 is 200 Pa ⁇ s or less. From this, it can be seen that the adhesive composition of the present invention is excellent in extrusion moldability and in embedding property (waterproof property).
  • Example 10 Si and Mg were detected by elemental analysis. Moreover, the transmittance
  • the adhesive composition of Example 10 has a transmittance of 20% or more at a thickness of 0.05 mm.
  • Example 11 and Reference Example 1 had a slightly high shear viscosity at a shear rate of 100 s ⁇ 1 and failed in the waterproof test. However, if the thickness of the adhesive layer is increased or the heat shrinkage temperature is high, it is presumed that the flowability of the adhesive layer at the time of thermal shrinkage is good and may be usable.
  • Comparative Example 1 and Comparative Example 2 do not contain an organically treated silicate.
  • Comparative Example 1 the viscosity at a low shear rate is too low and the extrusion moldability is unacceptable.
  • Comparative Example 2 the extrusion moldability is good, but the flowability of the resin is poor and the waterproof test fails.
  • Comparative Example 3 contains an organically treated silicate, but the shear viscosity is low at a shear rate of 0.1 s ⁇ 1 and the press moldability is unacceptable.
  • Comparative Examples 4 to 9 do not contain an organically treated silicate and contain an inorganic filler. In either case, the shear viscosity is low at a shear rate of 0.1 s ⁇ 1 and the press moldability is unacceptable. In addition, the transmittance of light with a wavelength of 850 nm is less than 30%, and it can be seen that the inorganic filler not subjected to organic treatment has poor dispersibility with respect to the thermoplastic resin. In Comparative Example 9 in which the content of the inorganic filler (layered silicate) was increased, the shear viscosity was increased at a shear rate of 0.1 s -1 compared to Comparative Example 8, but the extrusion moldability was unacceptable. It is enough. On the other hand, the waterproof test fails because the shear viscosity increases at a shear rate of 100 s ⁇ 1 .

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Abstract

熱収縮時の埋まり性を良好として被処理基材との密着性を向上できるとともに、押出成形時の接着剤層の厚みばらつきを低減できる熱回復物品を提供する。１９０℃、２．１６ｋｇ荷重でのメルトフローレートが１５ｇ／１０分以上１０００ｇ／１０分以下の熱可塑性樹脂と、有機処理層状珪酸塩とを有し、温度１５０℃剪断速度０．１ｓ－１での剪断粘度が１０００Ｐａ・ｓ以上である接着剤組成物からなる接着剤層と、前記接着剤層の外周に外層を有する多層熱回復物品。接着剤組成物の温度１５０℃剪断速度１００ｓ－１での剪断粘度が２００Ｐａ・ｓ以下であると、より好ましい。

Description

多層熱回復物品
　本発明は内面に接着剤層を有する多層熱回復物品に関する。
　径方向に熱収縮性を有する熱収縮チューブ、熱収縮キャップ等の熱回復物品は、絶縁電線の接続部や各種機器内配線の端末処理、金属管の防水、防食等のための被覆等に使用されている。たとえば熱収縮チューブを絶縁電線の接続部にかぶせて加熱すると、熱収縮チューブが接続部分の形状に沿って収縮して密着するため外傷等から保護できる。防水等のため接続部分に高度の密着性が要求される場合は内面に接着剤層を設けた接着剤つきの熱収縮チューブが用いられる。たとえば特許文献１には、内面に接着剤組成物層が形成された熱回復物品が記載されている。接着剤層には、エチレン－酢酸ビニル共重合体（ＥＶＡ）、エチレン－エチルアクリレート共重合体（ＥＥＡ）、ポリアミド樹脂等のホットメルト接着剤が用いられる。
　接着剤層を有する熱収縮チューブは、外層と内層（接着剤層）とをそれぞれチューブ状に押出成形した後、加熱下で径方向に膨張（拡径）し、冷却してその形状を固定することで製造される。押出成形後に電離性放射線を架橋して外層材料を架橋することもある。使用時には被処理基材の外側に熱収縮チューブを被覆した後、加熱して外側を熱収縮させると同時に、内側の接着剤層を流動させて被処理基材と外層との間を埋めて密着させる。特許文献２には、接着剤層を二層の熱可塑性樹脂層とした熱収縮チューブが記載されている。
特開２０００－１２９０４２号公報 特開平８－２３００３７号公報
　熱回復物品の内層に使用される接着剤層には、熱収縮時には容易に被着体と密着して埋まり性を確保する必要があるため、流動性が高いことが要求される。しかし流動性が高すぎると熱回復物品を押出成形する際に接着剤層の形状が安定せず、接着剤層の厚みばらつきが大きくなる。特に接着剤層の内径が小さい場合には接着剤層内部の空洞が埋まり、拡径作業が困難となる可能性がある。
　本発明は上記の問題に鑑みてなされたものであり、熱収縮時の埋まり性を良好として被処理基材との密着性を確保できるとともに、押出成形時の接着剤層の厚みばらつきを低減できる熱回復物品を提供することを課題とする。
　本発明は、温度１９０℃、荷重２．１６ｋｇでのメルトフローレートが１５ｇ／１０分以上１０００ｇ／１０分以下の熱可塑性樹脂と、有機処理層状珪酸塩とを有し、温度１５０℃、剪断速度０．１ｓ－１での剪断粘度が１０００Ｐａ・ｓ以上である接着剤組成物からなる接着剤層と、前記接着剤層の外周に外層を有する多層熱回復物品である。
　温度１９０℃、荷重２．１６ｋｇでのメルトフローレートが１５ｇ／１０分以上１０００ｇ／１０分以下の熱可塑性樹脂を接着剤組成物に含有することにより、流動性が良好な接着剤層を得られ、熱収縮時の被処理基材への密着性が向上する。また有機処理層状珪酸塩を接着剤組成物に含有し、温度１５０℃、剪断速度０．１ｓ－１での剪断粘度を１０００Ｐａ・ｓ以上とすることで押出成形時の接着剤層の流動性を抑制でき、接着剤層の厚みばらつきを低減できる。　
　本発明により、熱収縮時の埋まり性を良好として被処理基材との密着性を向上できるとともに、押出成形時の接着剤層の厚みばらつきを低減できる熱回復物品を得ることができる。
本発明の熱回復物品の一例を示した断面模式図である。
　図１は本発明の熱回復物品の一例を示した断面模式図である。チューブ状の接着剤層１の外周に、外層２を有している。接着剤層１は、温度１９０℃、荷重２．１６ｋｇでのメルトフローレートが１５ｇ／１０分以上１０００ｇ／１０分以下の熱可塑性樹脂と、有機処理層状珪酸塩とを有する接着剤組成物からなる。
　メルトフローレート（ＭＦＲ）は樹脂の流動性を表す指標であり、ＪＩＳ Ｋ６７６０で規定された押出し形プラストメータを用いＪＩＳ Ｋ７２１０に準拠して温度１９０℃、荷重２．１６ｋｇの条件で測定したものである。接着剤組成物に使用する熱可塑性樹脂はＭＦＲが１５ｇ／１０分以上１０００ｇ／１０分以下のものであれば任意のものを使用できる。例えばエチレン－酢酸ビニル共重合体（ＥＶＡ）、ポリアミド、エチレン－エチルアクリレート共重合体（ＥＥＡ）、飽和共重合ポリエステル等が例示でき、外層の種類や被処理基材の種類に応じて任意のものを選択して使用できる。
　ＭＦＲが１０００ｇ／１０分を超える熱可塑性樹脂を使用した接着剤組成物は、流動性が大きすぎるので安定して押出成形するのが困難となる。またＭＦＲが１５ｇ／１０分未満の熱可塑性樹脂を使用した接着剤組成物は、熱収縮時の流動性が低下する。熱可塑性樹脂のＭＦＲは１００ｇ／１０分以上８００ｇ／１０分以下がより好ましい。
　上記の樹脂のなかでも、エチレン－酢酸ビニル共重合体及びポリアミドは、有機処理層状珪酸塩の分散性に優れるため特に好ましく使用できる。エチレン－酢酸ビニル共重合体、ポリアミドをそれぞれ単独で用いても良いし、両者を混合しても良い。エチレン－酢酸ビニル共重合体として、酢酸ビニル含有量が１２質量％以上４６質量％以下のものが特に好ましい。酢酸ビニル含有量が１２質量％以上であれば有機処理層状珪酸塩の分散が容易となる。一方４６質量％より高くなると材料の固着が発生し、取扱いが困難となる。
　有機処理層状珪酸塩とはモンモリロナイト、ベントナイト、スメクタイト等の層状珪酸塩（粘土鉱物、クレー）を有機処理したものである。層状に積層した珪酸塩平面の間には、マグネシウムイオン、ナトリウムイオン、カルシウムイオン等の中間層カチオンが存在して層状の結晶構造を保っている。有機処理することでこの中間層カチオンが有機カチオンとイオン交換される。有機化合物が珪酸塩平面の表面に化学的に結合して層間に導入（インターカレーション）されることで珪酸塩平面間の層間距離が大きくなり、熱可塑性樹脂への分散性が向上する。層状珪酸塩としては天然品、合成品のいずれも使用できる。
　有機処理層状珪酸塩を熱可塑性樹脂に分散させて接着剤組成物の粘度を調整する。温度１５０℃、剪断速度０．１ｓ－１での剪断粘度を１０００Ｐａ・ｓ以上とする。なお粘度は回転式レオメーターで測定した値とする。
　押出成形時にダイスを通過する際、接着剤組成物には高い剪断応力がかかり流動性が高くなっている。しかしダイスを通過した後は接着剤組成物にかかる剪断応力は低減する。
この状態での接着剤組成物の粘度が低いとダイスを通過した後で接着剤層が変形して厚みばらつきが生じたり内部の空洞部分が埋まったりする。しかし温度１５０℃、剪断速度０．１ｓ－１での剪断粘度を１０００Ｐａ・ｓ以上とすると、ダイスを通過した直後に接着剤組成物の粘度が高くなるためダイス通過後の接着剤層の流動を抑えることができ、厚みばらつきを低減できる。
　接着剤組成物の温度１５０℃、剪断速度１００ｓ－１での剪断粘度を２００Ｐａ・ｓ以下とすると好ましい。上記のように低剪断速度域での粘度を高くすると押出成形性が良好となるが、高剪断速度域での粘度も高いままであると熱収縮時の流動性が低下して良好な密着性が得られないからである。
　接着剤組成物の３００℃での熱減量が１％以上であると好ましい。接着剤組成物には有機処理層状珪酸塩が含まれる。この有機処理層状珪酸塩を３００℃に加熱すると有機処理層状珪酸塩に含まれる有機化合物が分解して減量するため、３００℃での熱減量は有機処理層状珪酸塩に含まれる有機化合物量の目安となる。有機処理珪酸塩に含まれる有機化合物量は２０％～６０％とすることが好ましい。有機化合物含有量が少ない有機処理層状珪酸塩は熱可塑性樹脂への分散性が低下し、層状珪酸塩を微分散させることが難しい。なお３００℃での熱減量は熱分析装置で４００℃まで１０℃／分で温度を上昇させて測定し、５０℃の質量を基準にして３００℃時の質量減を算出した値である。
　接着剤組成物中に有機処理層状珪酸塩が含まれることは熱減量測定で確認できる。また有機処理層状珪酸塩はケイ素（Ｓｉ）及びマグネシウム(Ｍｇ)を含むため、接着剤組成物を元素分析してＳｉ、Ｍｇの存在を確認することによっても、有機処理層状珪酸塩の存在を確認することができる。
　接着剤組成物の１１０℃での貯蔵弾性率が０．１ＭＰａ以下であると好ましい。貯蔵弾性率は回転式レオメーターの振動測定において、歪を０．００１％から１０％まで変化させて測定し、０．１％歪時の貯蔵弾性率の値とする。貯蔵弾性率が０．１ＭＰａよりも高いと応力を加えても形状を維持するため、外層収縮時の接着層の埋まり性が悪化する。０．１ＭＰａ以下であると外層収縮時に接着層が容易に溶融するため外層収縮時の埋まり性が良い。
　有機処理層状珪酸塩の含有量は、温度１５０℃、剪断速度０．１ｓ－１での剪断粘度が１０００Ｐａ・ｓ以上となるように任意に調整する。熱可塑性樹脂１００質量部に対して有機処理層状珪酸塩を１質量部以上２０質量部以下含有させると良好に粘度を調整でき、好ましい。
　有機処理層状珪酸塩が熱可塑性樹脂に良好に分散していることは、波長８５０ｎｍの光の透過率を指標として判断できる。換算厚み１．０ｍｍでの波長８５０ｎｍの光の透過率が３０％以上であれば有機処理層状珪酸塩が良好に微分散していると推定される。なお有機処理していない層状珪酸塩を使用した場合は分散性が良好でないため換算厚み１．０ｍｍでの波長８５０ｎｍの光の透過率は３０％未満となると推定される。
　接着剤組成物中にカーボン等の黒色フィラーを混合して黒色とした場合は、換算厚み１．０ｍｍでの波長８５０ｎｍの光の透過率は３０％以上とならない。しかし換算厚みを０．０５ｍｍとすると波長８５０ｎｍの光の透過率は２０％以上となる。
　接着剤組成物には、上記の熱可塑性樹脂、有機処理層状珪酸塩以外の添加物を混合しても良い。例えば酸化防止剤、着色剤、滑材、熱安定剤、紫外線吸収剤等が添加物として使用される。これらの材料はオープンロール、加圧ニーダー、単軸混合機、二軸混合機等任意の混合機で混合して接着剤組成物を作成する。
　多層熱回復物品の外層には従来の熱収縮チューブに用いられている任意の材料を用いることができる。外層を構成する樹脂組成物は、ポリエチレン、ポリエステル、ポリアミド及びフッ素樹脂からなる群から選ばれる１種以上を樹脂成分とし、必要に応じて難燃剤、酸化防止剤、着色剤、滑材、熱安定剤、紫外線吸収剤等を混合したものとする。
　外層を構成する樹脂組成物と接着剤層を構成する接着剤組成物とを既知の溶融押出成形機を用いて押出成形して多層押出成形品を得ることができる。この多層押出成形品を融点以上の温度に加熱した状態でチューブ内に圧縮空気を導入する等の方法により所定の外形に膨張した後、冷却して形状を固定して多層熱回復物品が得られる。押出成形した後に外層材料を架橋すると耐熱性に優れる多層熱回復物品が得られる。架橋方法としては電離放射の照射による架橋、化学架橋、熱架橋等の方法を用いることができる。
　多層熱回復物品の形状は任意に設計することができる。押出成形時（膨張前）において外層の内径が１．０ｍｍ～３０ｍｍ、外層の肉厚が０．１ｍｍ～１０ｍｍ、接着剤層の厚みが０．１ｍｍ～１０ｍｍ程度、接着剤層の内径が０．１ｍｍ～８．５ｍｍ程度とするのが一般的である。本発明の多層熱回復物品は接着剤層の押出成形性に優れているため、特に接着剤層の内径が１．０ｍｍ以下と小さい場合でも良好に押出成形可能である。なお接着剤層のみをチューブ状に押出成形したものを膨張した外層チューブ内部にセットし、収縮させて使うことも可能である。
　本発明の多層熱回復物品としては、熱収縮チューブ、熱収縮キャップが含まれる。熱収縮チューブはチューブ状のものであり、長尺のものであっても、適当な長さに切断したものでも良い。熱収縮キャップとは、適当な長さに切断した熱収縮チューブの片端を加熱収縮して閉じたものである。
　次に、本発明を実施例に基づいてさらに詳細に説明する。実施例は本発明の範囲を限定するものではない。
　（実施例１～１１、参考例１、比較例１～９）
　（接着剤組成物の作成、押出成形性の評価）
　表１、表２に示す配合処方の熱可塑性樹脂とフィラー、及び酸化防止剤を溶融混合して接着剤組成物を作製した。得られた接着剤組成物を内層（接着剤層）とし、融点１２５℃のポリエチレンを外層として外層内径２．８ｍｍ、外層厚み０．９ｍｍ、内層（接着剤層）内径０．６ｍｍ、内層（接着剤層）厚み１．０ｍｍのチューブ状二層押出成形品を作製した。適当な長さに切断した押出成形品の一方の端から空気を入れ、逆側の端から空気が出てくることを確認できたものを合格とした。接着剤層の厚みばらつきが大きいとチューブ内部が接着剤で埋まって閉じてしまうため、空気が通り抜けることができない。
　（熱収縮チューブの製造）
　押出成形品に電離放射線を照射して外層を架橋した後、外層の外径が７．５ｍｍとなるように膨張させた後冷却して形状を固定して熱収縮チューブを得た。なお接着剤層には架橋しない程度の量の酸化防止剤が含まれているため架橋は阻害される。
　（熱収縮チューブの評価：防水試験）
　絶縁電線１本と絶縁電線４本とを溶接したハーネスの溶接部分に熱収縮チューブをかぶせ、１８０℃の恒温槽中で床面に水平に置き、９０秒加熱し収縮させて熱収縮チューブと溶接部分とを密着させた。このサンプルを水中に入れ、絶縁電線１本の片端から２００ｋＰａの空気を３０秒間吹き込み、水中でのバブル発生の有無を確認した。バブルが発生しないものを合格、バブルが発生したものを不合格とした。
　熱収縮チューブから外層を剥離して内層（接着剤層）のみとし、以下に示す一連の評価を行った。
　（剪断粘度測定）
　回転式レオメーター（アントンパール(株)製ＲＣＭ３０２）を用いて温度１５０℃での剪断粘度を測定した。剪断速度０．１ｓ－１のときの剪断粘度を剪断粘度１、剪断速度１００ｓ－１のときの剪断粘度を剪断粘度２とした。
　（貯蔵弾性率測定）
　回転式レオメーター（アントンパール(株)製ＲＣＭ３０２）を用いて歪を０．００１％から１０％まで変化させて振動測定を行い、０．１％歪時の貯蔵弾性率を測定した。
　（３００℃熱減量測定）
　得られた接着剤組成物の熱減量を熱分析装置で測定した。室温から４００℃まで１０℃／分で温度上昇し、５０℃の質量を基準として３００℃での質量減を算出した。
　（透過率測定）
　接着剤組成物を温度１５０℃でプレス加工して厚み１．０ｍｍのシートを作成し、分光光度計を用いて波長８５０ｎｍの光の透過率を測定した。なお実施例１０と比較例８の接着剤組成物にはカーボンブラックが入っており黒色であるため、厚み０．０５ｍｍのシートを作成して同様に測定した。
　（元素分析）
　エネルギー分散型Ｘ線分光法で接着剤組成物の元素分析を行った。Ｍｇ、Ｓｉ、Ｃａのうち含有するものを検出した。以上の結果を表１及び表２に示す。


















Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
　（脚注）
　ＥＶＡ１：ＭＦＲ１５０ｇ／１０分、酢酸ビニル含有量２８質量％のエチレン－酢酸ビニル共重合体
　ＥＶＡ２：ＭＦＲ８００ｇ／１０分、酢酸ビニル含有量２８質量％のエチレン－酢酸ビニル共重合体
　ＥＶＡ３：ＭＦＲ１５０ｇ／１０分、酢酸ビニル含有量１９質量％のエチレン－酢酸ビニル共重合体
　ＥＶＡ４：ＭＦＲ２ｇ／１０分、酢酸ビニル含有量５質量％のエチレン－酢酸ビニル共重合体
　ポリエチレン：ＭＦＲ１４５ｇ／１０分、密度０．９１５の低密度ポリエチレン
　有機処理層状珪酸塩１：塩化ジメチルジステアリルアンモニウムで処理した層状珪酸塩　有機処理層状珪酸塩２：塩化ベンジルジメチルステアリルアンモニウムで処理した層状珪酸塩
　有機処理膨潤性雲母：タルクから合成した合成フッ素雲母を塩化ジメチルジステアリルアンモニウムで処理したもの
　層状珪酸塩：上記有機処理層状珪酸塩１に使用した層状珪酸塩
　炭酸カルシウム：白石カルシウム(株)製、白艶華ＣＣＲ
　ワラストナイト：キンセイマテック(株)製、ＳＨ１８００
　タルク：日本タルク(株)製　ＭＩＣＲＯ ＡＣＥ ＳＧ９５
　カーボンブラック：算術平均粒子径２４ｎｍ、窒素吸着比表面積９３ｍ２／ｇ、嵩密度３６０ｋｇ／ｍ３のカーボンブラック
　実施例１～１０の接着剤組成物は、押出成形性に優れており、また防水性試験にも合格している。これらの接着剤組成物には有機処理層状珪酸塩が樹脂１００質量部に対して１質量％以上２０質量％以下含まれている。接着剤組成物の剪断速度０．１ｓ－１のときの剪断粘度はいずれも１０００Ｐａ・ｓ以上であり、剪断速度１００ｓ－１のときの剪断粘度は２００Ｐａ・ｓ以下である。このことから本発明の接着剤組成物が、押出成形性に優れると共に埋まり性（防水性）にも優れることがわかる。
　実施例１～１０のすべてにおいて、元素分析でＳｉ及びＭｇが検出されている。また波長８５０ｎｍの光の透過率は実施例１０を除くすべてで厚み１．０ｍｍで３０％以上であり、有機処理層状珪酸塩が良好に分散していることがわかる。なお実施例１０の接着剤組成物は厚み０．０５ｍｍでの透過率が２０％以上である。
　実施例１１及び参考例１の接着剤組成物は剪断速度１００ｓ－１のときの剪断粘度がやや高く、防水試験で不合格となった。しかし接着剤層の厚みを厚くしたり加熱収縮温度が高い条件であれば熱収縮時の接着剤層の流れ性は良好となり使用可能となる場合もあると推測される。
　比較例１、比較例２の接着剤組成物には有機処理珪酸塩が含まれていない。比較例１は低剪断速度での粘度が低すぎて押出成形性が不合格である。比較例２は、押出成形性は良好であるが樹脂の流れ性が悪く防水試験で不合格となる。比較例３には有機処理珪酸塩が含まれているが、剪断速度０．１ｓ－１のときの剪断粘度が低く押成形性が不合格である。
　比較例４～９は有機処理珪酸塩を含まず、無機フィラーを含んでいる。いずれも剪断速度０．１ｓ－１のときの剪断粘度が低く押成形性が不合格である。またいずれも波長８５０ｎｍ光の透過率が３０％未満であり、有機処理していない無機フィラーは熱可塑性樹脂に対する分散性が悪いことがわかる。無機フィラー（層状珪酸塩）の含有量を多くした比較例９は、比較例８に比べると剪断速度０．１ｓ－１のときの剪断粘度が上がっているが押出成形性は不合格であり不十分である。一方剪断速度１００ｓ－１のときの剪断粘度が高くなることから防水性試験が不合格となる。
　１接着剤層
　２外層

Claims (9)

  1. 　１９０℃、２．１６ｋｇ荷重でのメルトフローレートが１５ｇ／１０分以上１０００ｇ／１０分以下の熱可塑性樹脂と、有機処理層状珪酸塩とを有し、温度１５０℃、剪断速度０．１ｓ－１での剪断粘度が１０００Ｐａ・ｓ以上である接着剤組成物からなる接着剤層と、前記接着剤層の外周に外層を有する多層熱回復物品。
  2. 　前記接着剤組成物の温度１５０℃、剪断速度１００ｓ－１での剪断粘度が２００Ｐａ・ｓ以下である、請求項１に記載の多層熱回復物品。
  3. 　前記接着剤組成物の３００℃での熱減量が１％以上である、請求項１又は２に記載の多層熱回復物品。
  4. 　前記接着剤組成物の１１０℃での貯蔵弾性率が０．１ＭＰａ以下である、請求項１～３のいずれか１項に記載の多層熱回復物品。
  5. 　前記有機処理層状珪酸塩の含有量は、前記熱可塑性樹脂１００質量部に対して１質量部以上２０質量部以下である、請求項１～４のいずれか１項に記載の多層熱回復物品。
  6. 　前記熱可塑性樹脂はエチレン－酢酸ビニル共重合体又は／及びポリアミドである、請求項１～５のいずれか１項に記載の多層熱回復物品。
  7. 　前記接着剤組成物の換算厚み１．０ｍｍでの波長８５０ｎｍの光の透過率が３０％以上である、請求項１～６のいずれか１項に記載の多層熱回復物品。
  8. 　前記接着剤組成物は黒色であり、換算厚み０．０５ｍｍでの波長８５０ｎｍの光の透過率が２０％以上である、請求項１～６のいずれか１項に記載の多層熱回復物品。
  9. 　前記外層が、ポリエチレン、ポリエステル、ポリアミド、及びフッ素樹脂からなる群から選ばれる１種以上を樹脂成分とする樹脂組成物からなる、請求項１～８のいずれか１項に記載の多層熱回復物品。
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US20150004408A1 (en) 2015-01-01
EP2905132A1 (en) 2015-08-12
JP2014069522A (ja) 2014-04-21
JP5711713B2 (ja) 2015-05-07
CN103974828A (zh) 2014-08-06
CN103974828B (zh) 2016-05-18
EP2905132A4 (en) 2016-06-01

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