WO2013129293A1 - ゴム積層樹脂複合体 - Google Patents
ゴム積層樹脂複合体 Download PDFInfo
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- WO2013129293A1 WO2013129293A1 PCT/JP2013/054714 JP2013054714W WO2013129293A1 WO 2013129293 A1 WO2013129293 A1 WO 2013129293A1 JP 2013054714 W JP2013054714 W JP 2013054714W WO 2013129293 A1 WO2013129293 A1 WO 2013129293A1
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- WIPO (PCT)
- Prior art keywords
- polyamide
- rubber
- resin
- weight
- filler
- Prior art date
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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
- 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
- B32B25/08—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 synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B38/0036—Heat treatment
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/121—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives by heating
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C65/00—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor
- B29C65/02—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/40—General aspects of joining substantially flat articles, e.g. plates, sheets or web-like materials; Making flat seams in tubular or hollow articles; Joining single elements to substantially flat surfaces
- B29C66/41—Joining substantially flat articles ; Making flat seams in tubular or hollow articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29C66/00—General aspects of processes or apparatus for joining preformed parts
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- B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined
- B29C66/712—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined the composition of one of the parts to be joined being different from the composition of the other part
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
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- B29C66/7212—Fibre-reinforced materials characterised by the composition of the fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
- B29C66/72141—Fibres of continuous length
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/72—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the structure of the material of the parts to be joined
- B29C66/721—Fibre-reinforced materials
- B29C66/7214—Fibre-reinforced materials characterised by the length of the fibres
- B29C66/72143—Fibres of discontinuous lengths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C66/00—General aspects of processes or apparatus for joining preformed parts
- B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
- B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
- B29C66/737—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined
- B29C66/7375—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured
- B29C66/73751—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the state of the material of the parts to be joined uncured, partially cured or fully cured the to-be-joined area of at least one of the parts to be joined being uncured, i.e. non cross-linked, non vulcanized
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
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- B29K2507/00—Use of elements other than metals as filler
- B29K2507/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2509/00—Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
- B29K2509/08—Glass
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- B32B2038/0052—Other operations not otherwise provided for
- B32B2038/0076—Curing, vulcanising, cross-linking
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
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- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2321/00—Characterised by the use of unspecified rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such 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
- 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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- C09J2477/00—Presence of polyamide
- C09J2477/006—Presence of polyamide in the substrate
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- 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]
- Y10T428/31725—Of polyamide
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- 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
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- Y10T428/31725—Of polyamide
- Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
- Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a rubber laminated resin composite. More specifically, the present invention relates to a rubber laminated resin composite in which rubber and a polyamide resin molding are vulcanized and bonded without using an adhesive.
- Japanese Patent Application Laid-Open No. H10-228867 discloses that after the surface treatment is performed on the surface of the resin so that the average surface roughness is 0.1 or more, an adhesive is applied to the treated surface to vulcanize and bond the rubber.
- An adhesion method for adhering resin to rubber has been proposed. However, this method requires a new process such as surface treatment of the resin surface in addition to the process of using the adhesive.
- An object of the present invention is to provide a rubber-laminated resin composite in which a polyamide-based resin molding and a rubber such as acrylic rubber or fluororubber are bonded with sufficient adhesive strength by a simplified process without using an adhesive. There is.
- the object of the present invention is to provide an aliphatic amine compound having an amine equivalent of 950 or less and 0.045 mmol or more, preferably 0.050 to 0.055 g per 1 g of polyamide resin in which a filler is blended in an amount of 0 to 70% by weight in the total amount of the polyamide resin.
- This is achieved by a rubber-laminated resin composite in which rubber is vulcanized and bonded to a polyamide resin molded product molded from a polyamide resin added at a ratio of 2.0 mmol, more preferably 0.065 to 1.5 mmol.
- the rubber-laminated resin composite according to the present invention comprises an aliphatic amine compound having an amine equivalent of 950 or less in a polyamide-based resin, and 0 to 70% by weight, preferably 0 to 50% by weight, based on the total amount of filler and polyamide-based resin. By adding it at a rate of 0.045 mmol or more per gram of polyamide resin blended by weight%, it was possible to show sufficient adhesion simply by vulcanizing and bonding rubber to a polyamine resin molding without using an adhesive. There is an effect.
- Polyamide resins include polyamide 66 (melting point 260 ° C.), polyamide 6 (220 ° C.), polyamide 610 (215 ° C.), polyamide 612 (220 ° C.), polyamide 11 (187 ° C.), polyamide 12 (same as above) 176 ° C), polyamide 46 (290 ° C), polyamide 6T / 6I (310 ° C), 6T / 66 (260-340 ° C), 6T / 6 (230-340 ° C), 9T (306 ° C) At least one of them and their alloys or blend resins are used, and any polyamide can be used.
- fillers such as glass fiber, carbon fiber, aramid fiber, metal fiber, etc. are blended, preferably glass fiber and carbon fiber are blended.
- the blending amount is not more than 70% by weight, preferably 15 to 50% by weight, based on the total amount with the polyamide resin.
- the glass fiber has a diameter of about 1 to 50 ⁇ m, preferably about 5 to 20 ⁇ m, and a length of about 1 to 50 mm, preferably about 1 to 10 mm. Is generally used. These glass fibers may be surface-treated with a binding agent that is a polymer emulsion or a silane coupling agent. Moreover, the unidirectional composite material which compounded glass fibers, such as E glass and T glass, with an epoxy resin, vinyl ester, etc. may be sufficient.
- the carbon fiber is generally a PAN-based carbon fiber having a diameter of about 1 to 50 ⁇ m and a length of about 1 to 50 mm. Pitch-based carbon fibers can also be used.
- An aliphatic amine compound is added to the polyamide resin.
- an aliphatic amine compound having an amine equivalent of 950 or less, preferably 250 or less is used. If an amine equivalent is used, the reactivity is poor and an improvement in adhesion cannot be expected. Even if the amine equivalent is within the specified range, if an aromatic amine compound is used, no effect of improving adhesiveness is observed as shown in Comparative Examples 4 to 5 below.
- the amine compound when the boiling point of the amine compound is too lower than the melting point of the polyamide-based resin, the amine compound volatilizes when added to the polyamide, and therefore, depending on the type of polyamide used, for example, the melting point is 260 ° C.
- the amine compound added to the polyamide 66 should have a boiling point of 120 ° C. or higher, preferably 150 ° C. or higher.
- Such an aliphatic amine compound is 0.045 mmol or more, preferably 0.050 to 2.0 mmol, more preferably 0.065 to 1.5 mmol, per 1 g of polyamide resin in which 0 to 70% by weight of the filler is blended with the polyamide resin. Used in proportions. If the aliphatic amine compound is used in a smaller proportion, the effect of improving adhesiveness is not observed.
- aliphatic amine compound examples include tetraethylenepentamine (boiling point 330 ° C.), norbornane diamine (same 226 ° C.), hexamethylenediamine dicarbamate (325.3 ° C.), ⁇ , ⁇ -diaminododecane (304 ° C.), amine
- a polyamine compound such as polyetheramine having an equivalent weight of 50 to 950 (at 260 ° C. or higher) is used.
- the polyether amine is a reaction product of polyether alcohol and ammonia, an aliphatic amine or an alicyclic amine.
- the polyamide-based resin and the aliphatic amine compound are kneaded by being melt-mixed at 190 to 330 ° C. using a twin screw extruder, a single screw extruder or the like together with the filler when the filler is blended.
- the polyamide-based resin is molded using an injection molding machine, an extruder, a blow molding machine, a vacuum molding machine, or the like.
- a rubber compound such as a fluorine rubber compound and an acrylic rubber compound is bonded, and if necessary, bonded as an organic solvent solution, for example, under the vulcanization conditions of the used rubber compound,
- press vulcanization at about 100 to 250 ° C for about 1 to 120 minutes, a rubber laminated resin composite in which the polyamide resin and the rubber layer formed to a thickness of about 0.01 to 10 mm are bonded with sufficient strength is obtained. It is done.
- polyol vulcanizable or peroxide crosslinkable fluororubber compound is used as the fluorororubber compound.
- the polyol vulcanizable fluororubber compound is a compound in which various compounding agents are blended with fluororubber vulcanized by a polyol vulcanizing agent.
- Peroxide-crosslinkable fluororubber compound is a compound in which various compounding agents are blended in fluororubber, generally fluororubber with iodine group and / or bromine group introduced as a terminal group. In this case, organic peroxide crosslinking is used. It is preferable to mix and use a polyfunctional unsaturated compound co-crosslinking agent represented by triallyl isocyanurate together with the agent.
- acrylic rubber compound examples include vinyl monomers having various crosslinkable groups such as an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and / or an alkoxyalkyl acrylate having an alkylene group having 2 to 8 carbon atoms.
- Compound containing various compounding agents in acrylic rubber obtained by copolymerizing a small amount of a functional halogen-containing vinyl monomer, a carboxyl group-containing vinyl monomer, an epoxy group-containing monomer, a hydroxyl group-containing monomer, and the like. In this case, various crosslinking agents according to the type of the crosslinkable group are used.
- an organic peroxide is used as a crosslinking agent.
- a polyfunctional unsaturated compound co-crosslinking agent is preferably used in combination.
- polyamide 66 Toray product CM3006; melting point 260 ° C
- side feeder to glass fiber Nitobo product CSX-3J-451S; diameter 11 ⁇ m, length 3 mm
- polyetheramine seriessman product JEFFAMINE T403; theoretical molecular weight
- an unvulcanized fluororubber compound or an unvulcanized acrylic rubber compound with the following composition is bonded to an amide resin molded flat plate and applied under conditions of 180 ° C. for 6 minutes (fluororubber compound) or 8 minutes (acrylic rubber compound). Pressure vulcanization was performed to obtain a rubber laminated resin composite having a rubber layer having a thickness of 6 mm.
- Fluoro rubber compound; Formulation Example I Fluoro rubber (DuPont product Viton E45) 100 parts by weight Calcium metasilicate 40 ⁇ MT carbon black 20 ⁇ Magnesium oxide (Kyowa Chemical Product Magnesia # 150) 6 ⁇ Calcium hydroxide 3 ⁇ Vulcanizing agent (DuPont product curative # 30) 2 ⁇ Vulcanization accelerator (the company's product curative # 20) 1 [Acrylic rubber compound; Formulation Example II] Acrylic rubber (Unimatec product PA-522HF) 100 parts by weight HAF carbon black 55 ⁇ Stearic acid 1 ⁇ Anti-aging agent (Shiraishi calcium product Nowguard 445) 2 2 Processing aid (Schil & Seilacher (GmbH & Co) Stratol WB212) 2 ⁇ Processing aid (Toho Chemical Industries product Phosphanol RL210) 0.5 ⁇ Amine vulcanizing agent (Unimatec Cheminox AC-6) 0.6 ⁇ Vulcanization accelerator (
- Example 2 In Example 1, the same amount of tetraethylenepentamine (theoretical molecular weight 189.3, functional group number 5, theoretical amine equivalent 38 g / mol, boiling point 330 ° C.) was used instead of polyetheramine.
- Example 3 In Example 1, the same amount of norbornanediamine (theoretical molecular weight 154, number of functional groups 2, theoretical amine equivalent 77 g / mol, boiling point 227 ° C.) was used instead of polyetheramine.
- Example 4 In Example 1, instead of polyetheramine, hexamethylenediamine dicarbamate (theoretical molecular weight 160, number of functional groups 2, theoretical amine equivalent 80 g / mol, boiling point 325.3 ° C.) was used in the same amount.
- Example 5 In Example 1, the same amount of ⁇ , ⁇ -diaminododecane (theoretical molecular weight 200.37, functional group number 2, theoretical amine equivalent 100 g / mol, boiling point 304 ° C.) was used instead of polyetheramine.
- Example 6 In Example 1, the same amount of the product JEFFAMINE D400 (theoretical molecular weight 400, number of functional groups 2, theoretical amine equivalent 200 g / mol, boiling point 260 ° C.) was used as the polyetheramine.
- Example 7 In Example 1, the amount of polyetheramine was changed to 10 parts by weight.
- Example 8 In Example 1, the amount of polyetheramine was changed to 1 part by weight.
- Example 9 In Example 1, the amount of polyetheramine was changed to 0.75 parts by weight.
- Example 10 In Example 1 in which 5 parts by weight of polyetheramine was used, no glass fiber was used and 100 parts by weight of polyamide 66 was used.
- Example 11 In Example 8 in which 1 part by weight of polyetheramine was used, no glass fiber was used and 100 parts by weight of polyamide 66 was used.
- Example 2 Comparative Example 2 In Example 1, the same amount of the product JEFFAMINE D2000 (theoretical molecular weight 2000, number of functional groups 2, theoretical amine equivalent 1000 g / mol, boiling point 260 ° C. or higher) was used as the polyetheramine.
- JEFFAMINE D2000 theoretical molecular weight 2000, number of functional groups 2, theoretical amine equivalent 1000 g / mol, boiling point 260 ° C. or higher
- Example 3 Comparative Example 3 In Example 1, the same amount of the product JEFFAMINE T5000 (theoretical molecular weight 5000, functional group number 3, theoretical amine equivalent 1667 g / mol, boiling point 260 ° C. or higher) was used as the polyetheramine.
- Example 4 Comparative Example 4 In Example 1, the same amount of 4,4′-diaminodiphenyl sulfone (theoretical molecular weight 154.1, functional group number 2, theoretical amine equivalent 77 g / mol) was used instead of polyetheramine.
- Example 1 Comparative Example 5 In Example 1, the same amount of 1,3-bis (3-aminophenoxy) benzene (theoretical molecular weight 292.1, functional group number 2, theoretical amine equivalent 146 g / mol) was used instead of polyetheramine.
- Example 6 Comparative Example 6 In Example 1, the amount of polyetheramine was changed to 0.6 parts by weight.
- Comparative Example 7 In Comparative Example 6 in which 0.6 parts by weight of polyetheramine was used, no glass fiber was used and 100 parts by weight of polyamide 66 was used.
- the rubber laminated resin composites obtained in the above Examples and Comparative Examples were measured for adhesive strength and rubber remaining area ratio by 90 ° peel test (based on JIS K6256 corresponding to ISO 813).
- the measurement results are shown in the following Tables 1 and 2 together with the amine compound weight per 1 g of the filler-containing polyamide-based resin and the amine mmol number.
- the amine mmol number (theoretical value) in 1 g of the filler-containing polyamide-based resin was calculated by the weight of the amine compound (g) ⁇ 1000 / amine equivalent (g / mol) in 1 g of the filler-containing polyamide-based resin.
Abstract
Description
カルボキシル基含有ビニル単量体、エポキシ基含有単量体、水酸基含有単量体等を少量共重合させたアクリルゴムに各種配合剤を配合したコンパウンドである。この場合には、架橋性基の種類に応じた各種架橋剤が用いられる。
スクリュー径Φ25mm、L/D=41の二軸押出機を用い、ポリアミド66(東レ製品CM3006;融点260℃)80重量部に対してサイドフィーダーからガラスファイバー(日東紡製品CSX-3J-451S;直径11μm、長さ3mm)20重量部を、また同ベント部からポリエーテルアミン(huntsman製品JEFFAMINE T403;理論分子量440、官能基数3、理論アミン当量147g/mol、沸点260℃以上)5重量部をそれぞれ投入し、270℃で溶融混合したポリアミド樹脂組成物を、射出成形機を用いてシリンダー温度280℃、金型温度80℃に設定して25×60×2mmのアミド樹脂成形平板を作成した。なお、理論アミン当量は、理論分子量/理論官能基数により算出され、純度は100%で計算を行った(以下同じ)。
〔フッ素ゴムコンパウンド;配合例I〕
フッ素ゴム(デュポン社製品バイトンE45) 100重量部
メタけい酸カルシウム 40 〃
MTカーボンブラック 20 〃
酸化マグネシウム(協和化学製品マグネシア♯150) 6 〃
水酸化カルシウム 3 〃
加硫剤(デュポン社製品キュラティブ♯30) 2 〃
加硫促進剤(同社製品キュラティブ♯20) 1 〃
〔アクリルゴムコンパウンド;配合例II〕
アクリルゴム(ユニマテック製品PA-522HF) 100重量部
HAFカーボンブラック 55 〃
ステアリン酸 1 〃
老化防止剤(白石カルシウム製品ナウガード445) 2 〃
加工助剤(Schil&Seilacher(GmbH&Co)ストラクトールWB212) 2 〃
加工助剤(東邦化学工業製品フォスファノールRL210) 0.5 〃
アミン加硫剤(ユニマテック製品ケミノックスAC-6) 0.6 〃
加硫促進剤(大内新興化学製品ノクセラーDT) 2 〃
実施例1において、ポリエーテルアミンの代わりに、テトラエチレンペンタミン(理論分子量189.3、官能基数5、理論アミン当量38g/mol、沸点330℃)が同量用いられた。
実施例1において、ポリエーテルアミンの代わりに、ノルボルナンジアミン(理論分子量154、官能基数2、理論アミン当量77g/mol、沸点227℃)が同量用いられた。
実施例1において、ポリエーテルアミンの代わりに、ヘキサメチレンジアミンジカーバメート(理論分子量160、官能基数2、理論アミン当量80g/mol、沸点325.3℃)が同量用いられた。
実施例1において、ポリエーテルアミンの代わりに、α,ω-ジアミノドデカン(理論分子量200.37、官能基数2、理論アミン当量100g/mol、沸点304℃)が同量用いられた。
実施例1において、ポリエーテルアミンとして同社製品JEFFAMINE D400(理論分子量400、官能基数2、理論アミン当量200g/mol、沸点260℃)が同量用いられた。
実施例1において、ポリエーテルアミン量が10重量部に変更されて用いられた。
実施例1において、ポリエーテルアミン量が1重量部に変更されて用いられた。
実施例1において、ポリエーテルアミン量が0.75重量部に変更されて用いられた。
ポリエーテルアミンが5重量部用いられた実施例1において、ガラスファイバーが用いられず、ポリアミド66が100重量部用いられた。
ポリエーテルアミンが1重量部用いられた実施例8において、ガラスファイバーが用いられず、ポリアミド66が100重量部用いられた。
実施例1において、ポリエーテルアミンが用いられなかった。
実施例1において、ポリエーテルアミンとして同社製品JEFFAMINE D2000(理論分子量2000、官能基数2、理論アミン当量1000g/mol、沸点260℃以上)が同量用いられた。
実施例1において、ポリエーテルアミンとして同社製品JEFFAMINE T5000(理論分子量5000、官能基数3、理論アミン当量1667g/mol、沸点260℃以上)が同量用いられた。
実施例1において、ポリエーテルアミンの代わりに、4,4′-ジアミノジフェニルスルホン(理論分子量154.1、官能基数2、理論アミン当量77g/mol)が同量用いられた。
実施例1において、ポリエーテルアミンの代わりに、1,3-ビス(3-アミノフェノキシ)ベンゼン(理論分子量292.1、官能基数2、理論アミン当量146g/mol)が同量用いられた。
実施例1において、ポリエーテルアミン量が0.6重量部に変更されて用いられた。
ポリエーテルアミンが0.6重量部用いられた比較例6において、ガラスファイバーが用いられず、ポリアミド66が100重量部用いられた。
Claims (10)
- アミン当量が950以下の脂肪族アミン化合物を、充填剤をポリアミド系樹脂との合計量中0~70重量%配合したポリアミド系樹脂1g当り0.045ミリモル以上となる割合で添加したポリアミド系樹脂より成形されたポリアミド系樹脂成型物に、ゴムが加硫接着されたゴム積層樹脂複合体。
- ポリアミド系樹脂が、ポリアミド66、ポリアミド6、ポリアミド610、ポリアミド612、ポリアミド11、ポリアミド12、ポリアミド46、ポリアミド6T/6I、6T/66、6T/6および9Tの少なくとも一種あるいはこれらのアロイまたはブレンド樹脂である請求項1記載のゴム積層樹脂複合体。
- 充填剤がガラスファイバーまたはカーボンファイバーである請求項1記載のゴム積層樹脂複合体。
- 脂肪族アミン化合物が、充填剤をポリアミド系樹脂との合計量中0~70重量%配合したポリアミド系樹脂1g当り0.050~2.0ミリモルの割合で用いられた請求項1記載のゴム積層樹脂複合体。
- アミン当量が250以下の脂肪族アミン化合物が用いられた請求項1記載のゴム積層樹脂複合体。
- 沸点120℃以上の脂肪族アミン化合物が用いられた請求項1または5記載のゴム積層樹脂複合体。
- 充填剤配合ポリアミド系樹脂が、ポリアミド系樹脂100~50重量%および充填剤0~50重量%よりなる組成を有している請求項1記載のゴム積層樹脂複合体。
- ゴムが、フッ素ゴムまたはアクリルゴムである請求項1記載のゴム積層樹脂複合体。
- ポリアミド系樹脂に、アミン当量が950以下の脂肪族アミン化合物を、充填剤をポリアミド系樹脂との合計量中0~70重量%配合したポリアミド系樹脂1g当り0.045ミリモル以上となる割合で配合したポリアミド系樹脂を成形した後、得られたポリアミド系樹脂成型物にゴムを加硫接着することを特徴とするゴム積層樹脂複合体の製造方法。
- ポリアミド系樹脂100~50重量%および充填剤0~50重量%よりなる組成を有する充填剤配合ポリアミド系樹脂が用いられる請求項9記載のゴム積層樹脂複合体の製造方法。
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JP2002220480A (ja) * | 2001-01-25 | 2002-08-09 | Tokai Rubber Ind Ltd | ポリアミド・防振ゴム複合体 |
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JPH09239905A (ja) * | 1996-03-12 | 1997-09-16 | Yokohama Rubber Co Ltd:The | ゴム/ポリアミド系樹脂積層体 |
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JP2006089565A (ja) | 2004-09-22 | 2006-04-06 | Uchiyama Mfg Corp | 樹脂とゴムの接着方法およびそれを用いた樹脂とゴムの複合製品。 |
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