WO2013047058A1 - 積層体、架橋物及び成形部材 - Google Patents

積層体、架橋物及び成形部材 Download PDF

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Publication number
WO2013047058A1
WO2013047058A1 PCT/JP2012/071812 JP2012071812W WO2013047058A1 WO 2013047058 A1 WO2013047058 A1 WO 2013047058A1 JP 2012071812 W JP2012071812 W JP 2012071812W WO 2013047058 A1 WO2013047058 A1 WO 2013047058A1
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Prior art keywords
acrylic elastomer
acrylic
mass
fluorine
elastomer
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Ceased
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PCT/JP2012/071812
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English (en)
French (fr)
Japanese (ja)
Inventor
孝史 河崎
萩原　尚吾
俊明 宮内
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Denka Co Ltd
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Denki Kagaku Kogyo KK
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Priority to US14/347,151 priority Critical patent/US10086593B2/en
Priority to ES12835867.8T priority patent/ES2660974T3/es
Priority to CN201280046917.4A priority patent/CN103842173B/zh
Priority to IN3165DEN2014 priority patent/IN2014DN03165A/en
Priority to EP12835867.8A priority patent/EP2762306B1/en
Publication of WO2013047058A1 publication Critical patent/WO2013047058A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00—Hoses, i.e. flexible pipes
    • F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B32B2250/248—All polymers belonging to those covered by group B32B25/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/56—Damping, energy absorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2581/00—Seals; Sealing equipment; Gaskets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1386—Natural or synthetic rubber or rubber-like compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
    • Y10T428/1393—Multilayer [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

  • the present invention relates to a laminate using an elastomer, a cross-linked product, and a molded member. More specifically, the present invention relates to a laminate of an acrylic elastomer and a fluorine elastomer, a crosslinked product, and a molded member.
  • Acrylic elastomers and their cross-linked products have excellent physical properties such as heat aging resistance, oil resistance, mechanical properties, and compression set properties, so hose members, seal members, and vibration-proof rubber members in the engine compartment of automobiles. Widely used as a material. In recent years, these automobile members have been demanded of materials having better heat aging resistance due to the influence of exhaust gas countermeasures and higher engine output.
  • a method of treating the surface of the fluorinated elastomer layer with a metallic sodium solution for example, see Patent Document 1
  • a method of performing a discharge treatment for example, Patent Document 2
  • a plasma processing method for example, see Patent Document 3
  • a laminate has been proposed in which a fluororesin having a specific structure is mixed with fluororubber to improve physical properties such as resistance to low temperature embrittlement and to improve adhesion to a non-fluororubber layer. (See Patent Documents 4 and 5).
  • Patent Document 4 the adhesion to non-fluorine rubber is improved by using a polyol-based cross-linking agent for cross-linking of the fluoro rubber, or by adding an onium salt or an amine compound to the fluoro rubber. It is disclosed. Furthermore, there is a laminate in which the adhesion between the fluoropolymer layer and the non-fluororubber layer is improved by adding an adhesive compounding agent having a specific structure to the non-fluororubber layer (see Patent Document 6).
  • the conventional techniques described above have the following problems. That is, the surface treatment as described in Patent Documents 1 to 3 complicates the manufacturing process and causes an increase in the manufacturing cost of a laminate such as a hose product. In addition, when the surface treatment is performed, the elastomer layer is deteriorated and the sealing performance of the laminate may be lowered.
  • Patent Documents 4 to 6 have a problem that a process for melting fluororubber or fluororesin at a high temperature is required in advance before forming a laminate, and the manufacturing process becomes complicated. . Furthermore, in the method described in Patent Document 6, an adhesive compounding agent is added to the non-fluororubber layer. In order to enhance the effect, further, 8-benzyl-1,8-diazabicyclo [5, 4,0] -7-undecenium chloride, epoxy resin, etc. need to be added, and there is a problem that the kind and amount of chemicals to be added increase.
  • the main object of the present invention is to provide a laminate, a cross-linked product and a molded member having excellent interlayer adhesion.
  • the laminate according to the present invention contains an acrylic elastomer having an epoxy group as a main component, and contains 1 to 5 parts by mass of an onium salt and 1 to 8 parts by mass of a polyol compound with respect to 100 parts by mass of the acrylic elastomer. It comprises at least an acrylic elastomer layer formed from an acrylic elastomer composition and a fluorine elastomer layer formed from a fluorine elastomer composition containing a polyol crosslinking agent.
  • the onium salt may be an organic ammonium salt and / or an organic phosphonium salt.
  • a polyhydroxy aromatic compound can also be used as the polyol compound.
  • the crosslinked product according to the present invention is obtained by crosslinking the above-described laminate.
  • the molded member according to the present invention is formed of the above-described laminate or cross-linked product, and is used as, for example, a hose, a seal part, or a vibration-proof rubber part.
  • the fluorine elastomer and the acrylic elastomer are co-crosslinked, a laminate, a crosslinked product and a molded member having excellent interlayer adhesion can be obtained.
  • FIG. 1 is a cross-sectional view showing a configuration example of a laminate according to this embodiment.
  • the laminated body 1 of this embodiment has a configuration in which an acrylic elastomer layer 11 and a fluorine elastomer layer 12 are laminated.
  • FIG. 1 shows a laminate having a structure in which the acrylic elastomer layer 11 and the fluorine elastomer layer 12 are laminated one by one.
  • the present invention is not limited to this, and 1 or The laminate 1 may be configured by laminating two or more acrylic elastomer layers 11 and one or two or more fluorine elastomer layers 12. In that case, the acrylic elastomer layer 11 and the fluorine elastomer layer 12 are alternately laminated.
  • the laminate 1 of the present embodiment may include a layer other than the acrylic elastomer layer 11 and the fluorine elastomer layer 12.
  • the acrylic elastomer layer 11 is obtained by molding an acrylic elastomer composition containing at least an acrylic elastomer having an epoxy group, an onium salt and a polyol compound into a layer or a film.
  • the “acrylic elastomer composition” means that 50% by mass or more of the blended elastomer is an acrylic elastomer.
  • the elastomer blended with the acrylic elastomer include hydrin rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene-propylene rubber, silicone rubber, chlorosulfonated polyethylene rubber and the like.
  • the acrylic elastomer having an epoxy group which is the main component of the acrylic elastomer composition forming the acrylic elastomer layer 11, is a copolymer of a (meth) acrylic acid alkyl ester and a crosslinkable monomer containing an epoxy group.
  • the “crosslinking site monomer” refers to a monomer (monomer) having a functional group constituting a crosslinking site (crosslinking point).
  • the acrylic elastomer having an epoxy group may be copolymerized with vinyl acetate, a crosslinkable monomer other than the epoxy group, or ethylene, if necessary.
  • (Meth) acrylic acid alkyl ester is the skeleton of acrylic elastomer, and the basic properties such as normal properties, cold resistance and oil resistance of the resulting acrylic elastomer composition are adjusted by selecting the type of acrylic ester. can do.
  • the “(meth) acrylic acid alkyl ester” here is synonymous with (meth) acrylate, and includes both methacrylic acid alkyl ester (methacrylate) and acrylic acid alkyl ester (acrylate).
  • alkyl methacrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and n-pentyl.
  • (Meth) acrylate isoamyl (meth) acrylate, n-hexyl (meth) acrylate, 2-methylpentyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) Examples include acrylate, n-dodecyl (meth) acrylate, and n-octadecyl (meth) acrylate.
  • acrylic acid alkyl ester examples include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxy
  • examples thereof include propyl acrylate, 2- (n-propoxy) propyl acrylate, and 2- (n-butoxy) propyl acrylate.
  • the (meth) acrylic acid alkyl ester constituting the acrylic elastomer having an epoxy group is not limited to the above-mentioned methacrylic acid alkyl ester or acrylic acid alkoxyalkyl ester.
  • these (meth) acrylic acid alkyl esters may be used alone or in combination of two or more.
  • the cold resistance and oil resistance of the acrylic elastomer composition and its cross-linked product obtained can be adjusted by adjusting the blending amount of these unsaturated monomers when copolymerizing.
  • the cold resistance can be improved by increasing the copolymerization ratio of n-butyl acrylate, and the copolymerization ratio of ethyl acrylate is increased. Then, oil resistance can be improved.
  • the crosslinkable monomer is copolymerized with (meth) acrylic acid alkyl ester in order to advance intermolecular crosslinking and adjust the hardness and elongation characteristics of the resulting acrylic elastomer.
  • a crosslinkable monomer containing an epoxy group is essential, and other crosslinkable monomers such as those having an active chlorine group or a carboxyl group can be used in combination as necessary.
  • crosslinkable monomer containing an epoxy group examples include glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, and methallyl glycidyl ether.
  • crosslinking monomer examples include those having an active chlorine group such as 2-chloroethyl vinyl ether, 2-chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate, allyl chloroacetate, acrylic acid, methacrylic acid, croton.
  • Some containing carboxyl groups such as acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, maleic acid monoalkyl ester, fumaric acid monoalkyl ester, maleic acid monocyclohexyl, fumaric acid monocyclohexyl, cinnamic acid .
  • Acrylic elastomers are susceptible to sharp deterioration of mechanical properties such as tensile strength and elongation at break due to the main chain being cut by the influence of heat and ultraviolet rays.
  • vinyl acetate tends to cause a cross-linking reaction, and the intermolecular cross-linking of the resulting acrylic elastomer can be adjusted by adjusting the blending amount thereof. Therefore, when vinyl acetate is copolymerized into the main chain of an acrylic elastomer as another crosslinkable monomer, even when the acrylic elastomer is thermally aged and the main chain is broken, the vinyl acetate becomes a crosslinkable molecule. Since the space can be cross-linked again, mechanical properties such as elongation of the acrylic elastomer can be maintained.
  • the acrylic elastomer used in the laminate 1 of the present embodiment can be obtained by copolymerizing the above-described monomers by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization.
  • the amount of the crosslinkable monomer is preferably 0.5 to 10% by mass, more preferably 1 to 5% by mass, and particularly preferably 1 to 4% by mass, based on the total amount of monomers constituting the acrylic elastomer. %.
  • the “blending monomer content” here is the total amount of the crosslinking monomer to be blended. For example, when only the crosslinking monomer containing an epoxy group is used, the blending monomer content is shown and contains an epoxy group. And when using other crosslinkable monomer together, those total amounts are shown.
  • the compounding amount of the crosslinkable monomer is less than 0.5% by mass of the total monomer amount constituting the acrylic elastomer, a sufficient crosslinking effect cannot be obtained when the laminate is crosslinked, and the strength of the crosslinked product May be insufficient.
  • the compounding quantity of a crosslinkable monomer exceeds 10 mass% of the total monomer amount, the hardness of a crosslinked product will become high and rubber elasticity may be lost.
  • the blending amount is preferably 20% by mass or less of the total amount of monomers constituting the acrylic elastomer.
  • the copolymerization amount of vinyl acetate is within this range, it is possible to suppress the deterioration of the mechanical properties while maintaining the heat aging resistance of the acrylic elastomer.
  • the acrylic elastomer used in the laminate 1 of the present embodiment may be copolymerized with other monomers that can be copolymerized with the above-described monomers within a range not impairing the object of the present invention.
  • Other monomers copolymerizable with the acrylic elastomer are not particularly limited.
  • alkyl vinyl ketone such as methyl vinyl ketone
  • vinyl and ether such as vinyl ethyl ether and allyl methyl ether
  • styrene ⁇ -Vinyl aromatic compounds
  • vinyltoluene vinylnaphthalene
  • vinyl nitriles such as acrylonitrile and methacrylonitrile
  • acrylamide propylene, butadiene, isoprene, pentadiene
  • vinyl chloride, vinylidene chloride, vinyl fluoride, fluorine And ethylenically unsaturated compounds such as vinylidene chloride, ethylene, and vinyl propionate.
  • the strength of the acrylic elastomer can be remarkably improved.
  • the blending amount of ethylene is desirably 50% by mass or less of the total amount of monomers constituting the acrylic elastomer.
  • the acrylic elastomer composition forming the acrylic elastomer layer 11 contains 1 to 5 parts by mass of an onium salt with respect to 100 parts by mass of the acrylic elastomer as the main component.
  • an onium salt to the acrylic elastomer composition, co-crosslinking of the fluorine elastomer and the acrylic elastomer becomes possible.
  • the content of the onium salt is less than 1 part by mass per 100 parts by mass of the acrylic elastomer, the adhesiveness of the acrylic elastomer layer 11 is lowered, and peeling occurs between the fluorine elastomer layer 12.
  • content of onium salt exceeds 5 mass parts per 100 mass parts of acrylic elastomers, the workability of the acrylic elastomer layer 11 will fall.
  • the onium salt content in the acrylic elastomer composition is preferably 2 to 5 parts by mass per 100 parts by mass of the acrylic elastomer, whereby the adhesive force and workability of the acrylic elastomer layer 11 can be further improved. .
  • the onium salt added to the acrylic elastomer composition is not particularly limited, and examples thereof include organic ammonium salts and organic phosphonium salts. Specific examples thereof include organic ammonium salts such as tetra-n-butylammonium chloride, trimethylphenylammonium chloride, trimethylstearylammonium chloride, trimethyllaurylammonium chloride, trimethylcetylammonium chloride, dimethyldistearylammonium chloride, Examples include tributylbenzylammonium chloride, tetra-n-butylammonium bromide, methyltriphenylammonium bromide, ethyltriphenylammonium bromide, trimethylphenylammonium bromide, trimethylbenzylammonium bromide, stearyltrimethylammonium bromide, tetrabutylammonium thiocyanate .
  • organic ammonium salts such as tetra-
  • organic phosphonium salt examples include tetra-n-butylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, hexyltriphenylphosphonium bromide, and benzyl.
  • Examples include triphenylphosphonium bromide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, 4-butoxybenzyltriphenylphosphonium bromide, allyltributylphosphonium chloride, 2-propynyltriphenylphosphonium bromide, methoxypropyltributylphosphonium chloride, and the like.
  • These onium salts such as organic ammonium salts and organic phosphonium salts may be used alone or in combination of two or more.
  • the acrylic elastomer composition for forming the acrylic elastomer layer 11 contains 1 to 8 parts by mass of a polyol compound with respect to 100 parts by mass of the acrylic elastomer. By containing the polyol compound within this range, the processing stability of the acrylic elastomer layer 11 can be improved.
  • the content of the polyol compound is less than 1 part by mass per 100 parts by mass of the acrylic elastomer, the effect of improving the Mooney scorch stability of the acrylic elastomer composition becomes insufficient.
  • content of a polyol compound exceeds 8 mass parts per 100 mass parts of acrylic elastomers, when it is set as the laminated body 1, the adhesiveness of the acrylic elastomer layer 11 will fall.
  • the content of the polyol compound in the acrylic elastomer composition is preferably 2 to 8 parts by mass per 100 parts by mass of the acrylic elastomer, whereby the adhesive force and workability of the acrylic elastomer layer 11 can be further improved. .
  • the polyol compound added to the acrylic elastomer composition is not particularly limited.
  • a crosslinking agent or a crosslinking accelerator may be added to the acrylic elastomer composition that forms the acrylic elastomer layer 11.
  • fillers, reinforcing agents, plasticizers, lubricants, anti-aging agents, stabilizers, silane coupling agents, and the like can be added depending on the purpose when put to practical use.
  • the crosslinking agent is not particularly limited, and those commonly used for crosslinking of acrylic rubber compositions can be added, but imidazole compounds are particularly suitable. Further, the addition amount of the crosslinking agent is not particularly limited, but is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the acrylic elastomer. It can be carried out.
  • imidazole compound used as the crosslinking agent examples include 1-methylimidazole, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-ethylimidazole.
  • the crosslinking accelerator adjusts the crosslinking rate, and can be added within a range that does not diminish the effects of the present invention. For example, 0.1 to 5 parts by mass per 100 parts by mass of the acrylic elastomer is sufficient. The effect of addition is obtained.
  • epoxy resin curing agents such as pyrolyzed ammonium salts, organic acids, acid anhydrides, amines, sulfur and sulfur compounds can be used.
  • filler and the reinforcing agent those used for usual rubber applications can be used, and examples thereof include carbon black, silica, clay, talc, calcium carbonate and the like.
  • the addition amount of these fillers and reinforcing agents is desirably 20 to 100 parts by mass in total with respect to 100 parts by mass of the acrylic elastomer from the viewpoint of the reinforcing effect of the acrylic elastomer.
  • plasticizers used for ordinary rubber applications can be used, and examples thereof include ester plasticizers, polyoxyethylene ether plasticizers, and trimellitate plasticizers.
  • the amount of the plasticizer added is desirably 50 parts by mass or less with respect to 100 parts by mass of the acrylic elastomer.
  • This acrylic elastomer composition contains a predetermined amount of the above-mentioned acrylic elastomer having an epoxy group, an onium salt and a polyol compound, and, if necessary, other components such as a crosslinking accelerator and a filler are added. And kneading at a temperature below the crosslinking temperature.
  • the blending time of the onium salt and the polyol compound is not limited when various compounding agents are added to the acrylic elastomer and kneaded, and before the acrylic elastomer layer 11 and the fluorine elastomer layer 12 are cross-linked. What is necessary is just to mix
  • a rubber kneading apparatus used for preparing the acrylic elastomer composition an apparatus for kneading, molding, and crosslinking the acrylic rubber composition can be used usually in the rubber industry. Specifically, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used. And the obtained acrylic elastomer composition is shape
  • the fluorine-based elastomer layer 12 is obtained by molding a fluorine-based elastomer composition containing at least a fluorine-based elastomer and a polyol crosslinking agent into a layer or a film.
  • the “fluorine-based elastomer composition” means that 50% by mass or more of the blended elastomer is a fluorine-based elastomer.
  • Examples of the elastomer blended together with the fluorinated elastomer include hydrin rubber, nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, ethylene-propylene rubber, silicone rubber, chlorosulfonated polyethylene rubber and the like.
  • the fluorine-based elastomer is a main component of the fluorine-based elastomer composition that forms the fluorine-based elastomer layer 12. And this fluorine-type elastomer should just have a fluorine atom and a polyol bridge
  • the fluorine-based elastomer composition that forms the fluorine-based elastomer layer 12 contains a polyol crosslinking agent.
  • the polyol cross-linking agent cross-links the same or different polymer chains of the fluoroelastomer, and by this cross-linking, the tensile strength of the fluoroelastomer layer can be improved and its elasticity is good. Can be.
  • the crosslinked fluorine-based elastomer obtained by crosslinking with a polyol-based crosslinking agent has a carbon-oxygen bond at the crosslinking point, and therefore has a small compression set and excellent moldability.
  • the blending amount of the polyol crosslinking agent is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 3 parts by mass, and more preferably 100 parts by mass of the fluoroelastomer as a main component.
  • the amount is preferably 1 to 2.5 parts by mass.
  • the blending amount of the polyol crosslinking agent is less than 0.2 parts by mass per 100 parts by mass of the fluorinated elastomer, the effect of crosslinking the composition is reduced, and the strength of the crosslinked product may be insufficient.
  • the compounding quantity of a polyol crosslinking agent exceeds 10 mass parts per 100 mass parts of fluorine-type elastomers, the hardness of a crosslinked material will become high and rubber elasticity may be lost.
  • polyol crosslinking agent blended in the fluorine elastomer composition a polyol compound generally known for fluorine elastomers can be used.
  • polyol compounds polyhydroxy compounds are preferable, and polyhydroxy aromatic compounds having excellent heat resistance are particularly preferable.
  • the kind thereof is not particularly limited, and for example, resorcinol, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4- Hydroxyphenyl) perfluoropropane, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxystilbene, 2,6-dihydroxyanthracene 2,2-bis (4-hydroxyphenyl) butane, 4,4-bis (4-hydroxyphenyl) valeric acid, 2,2-bis (4-hydroxyphenyl) tetrafluorodichloropropane, 4,4′-dihydroxy Diphenylsulfone, 4,4'-dihydroxydi Eniruketon, tri (4-hydroxyphenyl) methane, 3,3 ', 5,5'-tetrachloro bisphenol A, 3,3
  • a polyhydroxy compound is preferable in that the compression set of the crosslinked fluoroelastomer is small and the moldability is excellent, and a polyhydroxy aromatic compound is preferable in terms of excellent heat resistance, 2-bis (4-hydroxyphenyl) perfluoropropane is more preferred.
  • the polyhydroxy aromatic compound described above may be an alkali metal salt, an alkaline earth metal salt, or the like, but in the case of coagulating a fluoroelastomer copolymer using an acid, the polyhydroxy aromatic compound is used. It is preferred not to use a metal salt of the compound.
  • a crosslinking accelerator is blended in the fluorine elastomer composition together with the polyol crosslinking agent.
  • a crosslinking accelerator it is possible to promote the crosslinking reaction by promoting the formation of an intramolecular double bond in the dehydrofluoric acid reaction of the fluorine-based elastomer main chain.
  • the crosslinking accelerator for polyol-based crosslinking a compound having a property that is difficult to add to the fluorine-based elastomer main chain is preferable, and an onium compound is generally used.
  • the onium compound to be blended as the crosslinking accelerator is not particularly limited.
  • ammonium compounds such as quaternary ammonium salts, phosphonium compounds such as quaternary phosphonium salts, oxonium compounds, sulfonium compounds, cyclic amines, 1 Examples thereof include functional amine compounds, and among these, onium salts such as quaternary ammonium salts and quaternary phosphonium salts are preferable.
  • the onium salt is not specifically limited, For example, the same kind as the acrylic elastomer composition mentioned above can be used.
  • the addition amount of the crosslinking accelerator is preferably 0.1 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and still more preferably 100 parts by weight of the fluorine-based elastomer. Is 0.1 to 0.7 parts by mass.
  • the addition amount of the crosslinking accelerator is less than 0.1 parts by mass with respect to 100 parts by mass of the fluorinated elastomer, the desired effect of promoting the crosslinking rate cannot be obtained. Since the speed becomes too fast, scorch (initial crosslinking before the crosslinking process) and molding defects are likely to occur.
  • Various additives such as an auxiliary agent, an acid acceptor, a release agent, a conductivity imparting agent, a thermal conductivity imparting agent, a surface non-adhesive agent, a flexibility imparting agent, a heat resistance improving agent, and a flame retardant can also be blended.
  • one or more crosslinking agents and crosslinking accelerators other than the polyol-based crosslinking agent may be blended.
  • the above-mentioned fluorine-based elastomer composition is kneaded with a fluorine-based elastomer, a polyol cross-linking agent, and, if necessary, other compounding agents such as a cross-linking accelerator and a filler using a commonly used rubber kneading apparatus.
  • a rubber kneading apparatus a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.
  • the method of adding the onium salt is not particularly limited, but before the fluorine elastomer layer and the acrylic elastomer layer are cross-bonded, for example, a strong cross-linking adhesive is achieved by adding the fluorine elastomer and various compounding agents during kneading. can do.
  • the laminate 1 of the present embodiment enables the acrylic elastomer and the fluorine elastomer to be co-crosslinked by the addition of the onium salt, so that the acrylic elastomer layer 11, the fluorine elastomer layer 12, It is possible to improve the adhesion. Moreover, since the polyol compound which has a crosslinking retarding effect is added to the acrylic elastomer composition which comprises this laminated body 1, it is excellent also in Mooney scorch stability. Furthermore, since the laminated body 1 of this embodiment does not require pre-kneading at a high temperature, it can be manufactured by a simple process.
  • the crosslinked product of the present embodiment is obtained by crosslinking the laminate 1 of the first embodiment described above.
  • the acrylic elastomer layer 11 and the fluorine elastomer layer 12 are desirably crosslinked by bonding the elastomers at the interface. Therefore, in this embodiment, these layers are cross-linked in a superposed state to form a cross-linked product. Thereby, a laminated body with stronger interlayer adhesion can be obtained.
  • the crosslinking method is not particularly limited, and usual crosslinking methods such as press crosslinking, steam crosslinking, and electron beam crosslinking can be employed.
  • the crosslinking temperature and crosslinking time can be appropriately set according to the composition of each elastomer composition and the type of crosslinking agent, but are usually 100 to 200 ° C. and 1 to 10 hours.
  • the cross-linked product of the present embodiment cross-links the laminate of the first embodiment, the interlayer adhesion between the fluorine-based elastomer layer and the acrylic elastomer layer is improved.
  • the onium salt and the polyol compound are added to the acrylic elastomer layer, the laminate of the first embodiment described above is excellent in interlayer adhesion and processing stability. As a result, it is possible to realize a laminate cross-linked product in which a plurality of elastomer layers are integrated and firmly bonded without complicating the manufacturing process.
  • the molded member of the present embodiment is, for example, a seal part or a vibration-proof rubber part such as a rubber hose, a gasket, and a packing, and is formed by the laminate of the first embodiment or the cross-linked product of the second embodiment. Yes.
  • Examples of rubber hoses include transmission oil cooler hoses, engine oil cooler hoses, air duct hoses, turbo intercooler hoses, hot air hoses, radiator hoses, power steering hoses, fuel system hoses, drain systems for automobiles, construction machinery, hydraulic equipment, etc. There are hoses. As a configuration of these rubber hoses, a reinforcement yarn or a wire may be provided in the middle of the hose or the outermost layer of the rubber hose as is generally done.
  • Seal parts include engine head cover gasket, oil pan gasket, oil seal, lip seal packing, O-ring, transmission seal gasket, crankshaft, camshaft seal gasket, valve stem, power steering seal belt cover seal, etc. Fast joint boot materials and rack and pinion boot materials.
  • Anti-vibration rubber parts include, for example, a damper pulley, a center support cushion, and a suspension bush.
  • the molded member of this embodiment is formed of the laminate of the first embodiment or the cross-linked product of the second embodiment, the acrylic elastomer layer suppresses a decrease in cold resistance, and the fluorine elastomer layer The heat aging resistance can be improved. As a result, a molded member having excellent heat aging resistance and cold resistance can be realized at low cost.
  • the composition of the acrylic elastomer composition was changed to produce laminates of the examples and comparative examples, and the interlayer adhesion after crosslinking and the Mooney scorch stability of the acrylic elastomer composition were evaluated.
  • the acrylic elastomer A had a copolymer composition of glycidyl methacrylate monomer unit: 1.3 parts by mass, ethyl acrylate monomer unit: 50 parts by mass, and n-butyl acrylate monomer unit: 50 parts by mass.
  • the glycidyl methacrylate monomer was quantified by dissolving the raw rubber of the copolymer (before cross-linking adhesion) in chloroform and titrating with a perchloric acid acetic acid solution.
  • the other monomer unit components were quantified by nuclear magnetic resonance spectroscopy.
  • This acrylic elastomer B had a copolymer composition of vinyl acetate monomer unit: 20 parts by mass, n-butyl acrylate monomer unit: 80 parts by mass, and glycidyl methacrylate: 1.5 parts by mass.
  • the quantitative method of the glycidyl methacrylate monomer and the quantitative determination of other monomer unit components were performed by the same method as the acrylic elastomer A described above.
  • acrylic elastomer C is composed of 1.3 parts by weight of glycidyl methacrylate monomer unit, 50 parts by weight of ethyl acrylate monomer unit, 47 parts by weight of n-butyl acrylate monomer unit, and 3 parts by weight of ethylene monomer unit.
  • the polymer composition is composed of 1.3 parts by weight of glycidyl methacrylate monomer unit, 50 parts by weight of ethyl acrylate monomer unit, 47 parts by weight of n-butyl acrylate monomer unit, and 3 parts by weight of ethylene monomer unit.
  • the acrylic elastomer is the same method and conditions as the acrylic elastomer A described above, except that the composition of the monomer component that is the raw material of the acrylic elastomer is changed to ethyl acrylate: 5.5 kg and n-butyl acrylate: 5.5 kg. D was obtained.
  • This acrylic elastomer D had a copolymer composition of ethyl acrylate monomer units: 50 parts by mass and n-butyl acrylate monomer units: 50 parts by mass.
  • acrylic elastomers A to D and other materials described above were kneaded using an 8-inch open roll with the blending (mass ratio) shown in Tables 2 to 5 below, and Examples 1 to 17 and Comparative Examples 1 to 18 were mixed.
  • An acrylic elastomer composition was obtained.
  • these acrylic elastomer compositions (uncrosslinked) were formed into a sheet having a thickness of 2.5 mm to form an acrylic elastomer layer.
  • these acrylic elastomer layers and the above-mentioned fluorine elastomer layer are adhered to each other, and in that state, heat treatment is performed at 160 ° C. for 35 minutes by a steam heating type hot press, and each laminate of the examples and comparative examples A crosslinked product was obtained.
  • the reagents used in the examples and comparative examples shown in Tables 1 to 5 are as follows. Fluorine-based elastomer: Daiel G558 (manufactured by Daikin Industries, Ltd., containing a polyol cross-linking agent in the product) Magnesium oxide: Kyowa Mag 150 (manufactured by Kyowa Chemical Industry Co., Ltd.) ⁇ Calcium hydroxide: Special reagent grade (manufactured by Wako Pure Chemical Industries, Ltd.) ⁇ Carbon SRF: Asahi # 50 (Asahi Carbon Co., Ltd.) ⁇ Carbon HAF: Seast # 3 (Tokai Carbon Co., Ltd.) ⁇ Anti-aging agent: NOCRACK CD (manufactured by Ouchi Shinsei Chemical Co., Ltd.) ⁇ Stearic acid: LUNAC S-90 (manufactured by Kao Corporation) ⁇ Stearyltrimethylammonium bromide: Special reagent grade (man
  • Interlaminar adhesion was evaluated based on the peel strength obtained by performing a 180 ° peel test on each specimen using a tensile tester with a peel rate of 50 mm / min. In addition, the peeling mode of each test piece was observed, and evaluation was made with ⁇ indicating that material destruction occurred, ⁇ indicating partial material destruction, and ⁇ indicating peeling at the interface of the layers.
  • Mooney scorch stability About each acrylic elastomer composition of an Example and a comparative example, Mooney scorch time (t5) was measured on 125 degreeC measurement conditions according to JISK6300. It can be said that the greater the Mooney scorch time (t5), the better the Mooney scorch stability. In the case of the compound shown in Table 1, the fluorine-based elastomer composition has a Mooney scorch time (t5) of about 10 minutes, and there is no problem in processing stability. Only acrylic elastomer compositions for which a decrease in stability was a concern were evaluated.
  • Comparative Examples 1, 7, 8, and 9 had good Mooney scorch stability, but the adhesiveness was inferior to Examples 1 to 8. In Comparative Examples 2-6 and 11-17, the adhesion was good, but the Mooney scorch stability was poor. As described above, when the Mooney scorch stability is short, there is a possibility that processing defects may occur, and it becomes difficult to produce a laminate.

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  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Vibration Prevention Devices (AREA)
  • Springs (AREA)
  • Gasket Seals (AREA)
PCT/JP2012/071812 2011-09-26 2012-08-29 積層体、架橋物及び成形部材 Ceased WO2013047058A1 (ja)

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US14/347,151 US10086593B2 (en) 2011-09-26 2012-08-29 Laminate body, cross-linked product, and molded member
ES12835867.8T ES2660974T3 (es) 2011-09-26 2012-08-29 Cuerpo laminado, producto reticulado y elemento moldeado
CN201280046917.4A CN103842173B (zh) 2011-09-26 2012-08-29 层叠体、交联物以及成型构件
IN3165DEN2014 IN2014DN03165A (enExample) 2011-09-26 2012-08-29
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014231159A (ja) * 2013-05-28 2014-12-11 倉敷化工株式会社 積層ゴムホース

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6179217B2 (ja) * 2013-06-24 2017-08-16 日本ゼオン株式会社 ゴム積層体
PL3165360T3 (pl) * 2014-07-18 2019-10-31 Zeon Corp Laminat
JP6352791B2 (ja) 2014-12-11 2018-07-04 Ckd株式会社 コイル用シート、コイル、及びコイルの製造方法
JP6247629B2 (ja) * 2014-12-11 2017-12-13 Ckd株式会社 コイル用シートの製造方法、及びコイルの製造方法
CN106286824A (zh) * 2015-05-27 2017-01-04 无锡恩福油封有限公司 密封圈
JP6623800B2 (ja) * 2016-02-04 2019-12-25 横浜ゴム株式会社 マリンホース
JP7169191B2 (ja) * 2016-07-05 2022-11-10 デンカ株式会社 アクリルゴム組成物
US20180080585A1 (en) * 2016-09-19 2018-03-22 Contitech Mgw Gmbh Fluoroelastomer/epdm hose for cold-side charge air applications
DE102018111968A1 (de) * 2018-05-18 2019-11-21 Veritas Ag Fluidleitung zum leiten eines fluids
CN114502641B (zh) * 2019-10-16 2024-01-12 电化株式会社 丙烯酸酯橡胶、橡胶组合物及其交联物、橡胶软管及密封部件
US20230265228A1 (en) * 2019-10-16 2023-08-24 Denka Company Limited Acrylic rubber, rubber composition and crosslinked product thereof, rubber hose, and seal part
CN111792276A (zh) * 2020-06-08 2020-10-20 湖北海特尔科技有限公司 具有耐高温、阻燃与耐油的橡胶输送带及其制造工艺

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5970562A (ja) * 1982-10-15 1984-04-21 豊田合成株式会社 ゴム積層材
JPH0367637A (ja) 1989-08-08 1991-03-22 Nippon Valqua Ind Ltd フッ素樹脂とゴムとの接着方法
JP2002059486A (ja) 2000-08-17 2002-02-26 Asahi Glass Co Ltd フッ素樹脂フィルムと未加硫ゴムとの加硫接着方法
JP2004150457A (ja) * 2002-10-28 2004-05-27 Tokai Rubber Ind Ltd 燃料用ホース
WO2009020182A1 (ja) 2007-08-08 2009-02-12 Daikin Industries, Ltd. 含フッ素樹脂および架橋フッ素ゴムを含む熱可塑性樹脂組成物
JP2009234216A (ja) 2008-03-28 2009-10-15 Tokai Rubber Ind Ltd 燃料ホースの製法
JP2010042669A (ja) 2008-07-16 2010-02-25 Daikin Ind Ltd フッ素ゴム積層体およびその製造方法
JP2010253728A (ja) * 2009-04-22 2010-11-11 Daikin Ind Ltd フッ素樹脂層とエラストマー層からなる積層体
JP2011116004A (ja) 2009-12-02 2011-06-16 Daikin Industries Ltd フッ素ポリマー積層体の製造方法、それにより得られるフッ素ポリマー積層体、及び、非フッ素ゴム組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3337519A1 (de) 1982-10-15 1984-05-10 Japan Synthetic Rubber Co., Ltd., Tokyo Kautschuklaminat
JP2583444B2 (ja) * 1988-06-23 1997-02-19 日本ゼオン株式会社 ゴム積層体の製造方法
CA2063478A1 (en) * 1991-03-22 1992-09-23 Michael F. Novits Scorch extending curing/crosslinking compositions
US5508355A (en) * 1992-04-03 1996-04-16 E. I. Du Pont De Nemours And Company Vulcanizable fluorine-containing elastomer composition
JP3265345B2 (ja) * 1993-12-20 2002-03-11 東ソー株式会社 ゴム積層体
JPH1143503A (ja) * 1997-07-25 1999-02-16 Nippon Mektron Ltd 変性アクリル系ゴムの製造法
US20050000582A1 (en) 2002-10-28 2005-01-06 Tokai Rubber Industries, Ltd. Fuel hose
WO2008139967A1 (ja) 2007-05-07 2008-11-20 Daikin Industries, Ltd. フッ素ゴム層および非フッ素ゴム層からなる積層体およびその製造方法
CN101765497B (zh) * 2007-07-30 2013-05-29 旭硝子株式会社 固化性树脂组合物以及采用该组合物的透明层叠体及其制造方法
JP4968338B2 (ja) * 2007-08-08 2012-07-04 ダイキン工業株式会社 フッ素樹脂層とエラストマー層からなる積層体
CA2801156C (en) * 2010-06-09 2018-06-05 Denki Kagaku Kogyo Kabushiki Kaisha Laminate and vulcanized product thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5970562A (ja) * 1982-10-15 1984-04-21 豊田合成株式会社 ゴム積層材
JPH0367637A (ja) 1989-08-08 1991-03-22 Nippon Valqua Ind Ltd フッ素樹脂とゴムとの接着方法
JP2002059486A (ja) 2000-08-17 2002-02-26 Asahi Glass Co Ltd フッ素樹脂フィルムと未加硫ゴムとの加硫接着方法
JP2004150457A (ja) * 2002-10-28 2004-05-27 Tokai Rubber Ind Ltd 燃料用ホース
WO2009020182A1 (ja) 2007-08-08 2009-02-12 Daikin Industries, Ltd. 含フッ素樹脂および架橋フッ素ゴムを含む熱可塑性樹脂組成物
JP2009234216A (ja) 2008-03-28 2009-10-15 Tokai Rubber Ind Ltd 燃料ホースの製法
JP2010042669A (ja) 2008-07-16 2010-02-25 Daikin Ind Ltd フッ素ゴム積層体およびその製造方法
JP2010253728A (ja) * 2009-04-22 2010-11-11 Daikin Ind Ltd フッ素樹脂層とエラストマー層からなる積層体
JP2011116004A (ja) 2009-12-02 2011-06-16 Daikin Industries Ltd フッ素ポリマー積層体の製造方法、それにより得られるフッ素ポリマー積層体、及び、非フッ素ゴム組成物

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2762306A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014231159A (ja) * 2013-05-28 2014-12-11 倉敷化工株式会社 積層ゴムホース

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