JP2004168046A - Composite material and its manufacturing process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material, which is excellent in heat resistance and recycling efficiency and good in inter-layer coherence, and its manufacturing process. <P>SOLUTION: The composite material is composed of, (A) a layer of thermoplastic resin or elastomer, and (B) a layer of a silicone modified thermoplastic elastomer obtained by vulcanizing a silicone rubber composition in a thermoplastic resin or elastomer. <P>COPYRIGHT: (C)2004,JPO

Description

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

  It is known that a composite having both characteristics can be obtained by combining a thermoplastic resin having excellent mechanical strength and dimensional stability with an elastomer having excellent flexibility and elasticity. Such composites are used in various forms such as hoses, connectors, sheets, tubes, cords, cables, and the like, and are used in automotive applications such as interior and exterior parts of automobiles and parts around engines. And architectural / construction applications, electric / electronic device applications, and the like. For example, Patent Literature 1 proposes a fuel hose in which an outer layer of a fluororesin hose is covered with a thermoplastic resin layer and a thermoplastic elastomer layer. However, the composite of the thermoplastic resin and the thermoplastic elastomer has a problem that the heat resistance of the thermoplastic elastomer portion is insufficient, and the composite cannot be used for a long time at a high temperature. Patent Literature 2 proposes a waterproof connector for automobiles in which a thermoplastic resin and silicone rubber are integrally molded. However, since silicone rubber cannot be heated and re-melted, it has a disadvantage that it cannot be recycled. Further, as a method for producing a composite, there is a method of bonding a thermoplastic resin layer and an elastomer layer using an adhesive, a primer or the like, but this method has a disadvantage that the operation is complicated.

On the other hand, silicone-modified thermoplastic elastomers obtained by vulcanizing a silicone rubber composition in a thermoplastic resin or a thermoplastic elastomer are known (see Patent Documents 3 and 4). Such silicone-modified thermoplastic elastomers include various hoses and tubes such as brake hoses, fuel hoses and water hoses; cable coating materials such as control cables and high tension cords; sealing parts such as connectors and grommets; ducts such as air ducts. Classes; Boots such as CVJ boots, rack & pinion boots, MacPherson strut covers, steering rod covers, etc .; O-rings, packings, water pump packings, timing belt cover seals, oil pan seals, engine head cover packings, engine head cover mounts, gaskets, etc. Belts such as timing belts or their covering materials; leaf spring bushing, door latch striker, safety belt ratchet, window glass steady rest roll, absorber -Rolls, bushings such as ball joint retainers, anti-vibration parts; Caps; Interior materials such as handles, grips, trims, console boxes, instrument panels, seats; Weather strips such as glass run channels, door seals, trunk seals, etc. It is being studied as a material for interior parts, exterior parts, and parts around engines. In addition, coating materials such as electric cables, optical cables, wires, cords, and ropes; sealing materials such as window seals and gaskets; construction and construction materials such as sheet materials such as waterproof sheets and plastic flooring; cables and cords. Coating materials such as printer ink hoses, electrical and electronic parts materials such as hoses and tubes such as washing machine water absorption / drainage tubes, tool materials such as handles and soft grips, and sports equipment materials such as balls and shoes. Application to general use is also being considered. However, when the silicone-modified thermoplastic elastomer contains a large amount of the silicone rubber composition, there is a disadvantage that the mechanical strength is reduced and the silicone-modified thermoplastic elastomer cannot be used depending on the application.
JP 2000-55248 A JP-A-9-165517 JP 2000-109696 A Japanese Patent Publication No. 2002-503366

The present inventors have conducted intensive studies to solve the above problems, and as a result, have reached the present invention.
That is, an object of the present invention is to provide a composite which is excellent in heat resistance and recyclability, and in which each layer is well adhered, and a method for producing the same.

The present invention provides (A) a thermoplastic resin layer or a thermoplastic elastomer layer,
(B) A composite comprising a silicone-modified thermoplastic elastomer layer obtained by vulcanizing a silicone rubber composition in a thermoplastic resin or a thermoplastic elastomer.
Further, the present invention provides a method for producing the composite, characterized in that a thermoplastic resin or a thermoplastic elastomer and a silicone-modified thermoplastic elastomer are heated and melted and simultaneously molded, and a thermoplastic resin or a thermoplastic elastomer. The present invention relates to a method for producing the composite, characterized in that one of the silicone-modified thermoplastic elastomers is heated and melted and molded, and then the other is heated and melted and molded on the surface.

  Since the composite of the present invention has a silicone-modified thermoplastic elastomer layer, it has excellent heat resistance and recyclability, and is suitable for hoses, connectors, and sheets. Further, according to the production method of the present invention, there is a feature that a composite in which each layer is well adhered can be produced with high productivity.

First, the composite of the present invention will be described.
The composite of the present invention is a laminate composed of (A) a thermoplastic resin layer or a thermoplastic elastomer layer and (B) a silicone-modified thermoplastic elastomer layer, and may have a two-layer structure or a multilayer structure. The thickness of each layer varies depending on the application and form and is not particularly limited, but is preferably in the range of 0.01 to 10 cm, more preferably 0.05 to 5 cm, and particularly preferably 0.05 to 2 cm. Further, the thicknesses of the (A) layer and the (B) layer may be the same or different. The thermoplastic resin or the thermoplastic elastomer of the layer (A) and the thermoplastic resin or the thermoplastic elastomer used for the layer (B) may be the same or different, but the layers (A) and (B) The same or the same type is preferable in terms of adhesion and adhesion. However, there is a combination having good adhesion even with different kinds such as a polyurethane elastomer and a nylon or a polyurethane elastomer and a polycarbonate resin.

  The thermoplastic resin or thermoplastic elastomer of the layer (A) is an organic resin that can be molded by heating and melting, and that can be replasticized by heating and melting after molding. Specific examples of this component include polyethylene (PE) resin, low density polyethylene (LDPE) resin, medium density polyethylene resin, high density polyethylene (HDPE) resin, ultrahigh molecular weight polyethylene (UHMPE) resin, ethylene and propylene, butene- Copolymers with α-olefins having 3 to 12 carbon atoms, such as 1, pentene-1, hexene-1,4-methylpentene-1, octene-1, and decene-1, polypropylene (PP) resin, propylene and butene Copolymer with α-olefin having 3 to 12 carbon atoms such as -1, pentene-1, hexene-1, 4-methylpentene-1, octene-1, decene-1, etc., ethylene-propylene-diene copolymer , Polymethylpentene resin (MPX), ethylene-methacrylate copolymer resin, ethylene and vinyl acetate, male Polyolefin resins such as copolymer resins with vinyl monomers such as acid anhydride and maleic anhydride; acrylic resins such as polymethyl methacrylate (PMMA) resin; polystyrene (PS) resin; high impact polystyrene (HIPS) Resin, acrylonitrile-butadiene-styrene (ABS) copolymer resin, acrylonitrile-styrene (AS) copolymer resin, acrylonitrile-acryl rubber-styrene (AAS) copolymer resin, acrylonitrile-ethylene propylene rubber-styrene (AES) Styrene-based vinyl resins such as copolymer resins; vinyl-based resins such as polyvinyl acetate resin, polyvinyl chloride (PVC) resin, polyvinylidene chloride (PVDC) resin, polyvinyl alcohol resin (PVA), and polytetrafluoroethylene resin (PTFE) resin; Polyester resins such as ribbutylene terephthalate (PBT) resin and polyethylene terephthalate (PET) resin; polyamide resins such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12; polyoxyalkylene resins such as polyacetal (POM); polycarbonate (PC) resin; modified polyphenylene ether (modified PPE) resin; polyvinyl acetate (PVAC) resin; polysulfide resin such as polysulfone (PSU) resin, polyethersulfone (PES) resin, polyphenylene sulfide (PPS) resin; (PAR) resin; polyamideimide (PAI) resin; polyetherimide (PEI) resin; polyetheretherketone (PEEK) resin; polyimide (PI) resin; Le (LCP) resin and copolymers thereof. Further, a thermoplastic polyurethane-based elastomer, a thermoplastic polyester-based elastomer, a thermoplastic polyamide-based elastomer, a thermoplastic polystyrene-based elastomer, a thermoplastic polyolefin-based elastomer, a thermoplastic polyfluoro-based elastomer, and a thermoplastic polyvinyl chloride-based elastomer can also be used. Among these, a polyamide resin, a polyester resin, a polycarbonate resin, a styrene-based vinyl resin, a polyolefin-based resin, a thermoplastic polyurethane-based elastomer, a thermoplastic polyester-based elastomer, a thermoplastic polyamide-based elastomer, and a thermoplastic polyolefin-based elastomer are preferable.

  Such thermoplastic resins and thermoplastic elastomers include organic lubricants, fluorine lubricants, non-crosslinkable silicone oils, and non-crosslinkable silicone gums in order to improve moldability, surface lubricity, and mold release properties. Etc. may be blended. Furthermore, other various additives and fillers can be blended. Examples of additives other than the lubricant include, for example, a strength improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a foaming agent, a crystal nucleating agent, an antistatic agent, a conductivity imparting agent, and a pigment. Coloring agents such as dyes and dyes, compatibilizers, crosslinking agents, flame retardants, mildewproofing agents, low-shrinking agents, thickeners, release agents, antifogging agents, blooming agents, and silane coupling agents. Examples of the filler include glass fiber, carbon fiber, glass cloth, calcium carbonate, mica, and talc.

  As the thermoplastic resin or thermoplastic elastomer used for the (B) layer, the same ones as those exemplified for the (A) layer are exemplified. Among these, polyester resins, polyamide resins, polyolefin resins, thermoplastic polyurethane elastomers, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and thermoplastic polyolefin elastomers are preferred. Examples of the polyester resin include a polybutylene terephthalate resin and a polyethylene terephthalate resin. Examples of the polyamide resin include nylon 6, nylon 66, and nylon 12 resins. Examples of the polyolefin-based resin include a polyethylene resin and a polypropylene resin.

  (B) The silicone rubber composition used in the layer includes an addition reaction-curable silicone rubber composition, an organic peroxide-curable silicone rubber composition, a condensation reaction-curable silicone rubber composition, and an ultraviolet-curable silicone rubber composition. Things. Among these, an addition reaction-curable silicone rubber composition is preferred. Specifically, (a) an organopolysiloxane having at least two alkenyl groups in one molecule and having a Williams plasticity of at least 30; A) an organosilicon compound having at least two silicon-bonded hydrogen atoms in one molecule, (c) a catalyst for hydrosilylation reaction, and (d) an addition reaction-curable silicone rubber composition containing fumed silica as a main component. Can be

Examples of the alkenyl group in the component (a) include alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, butenyl, pentenyl, hexenyl, and decenyl. Among these, a vinyl group or a hexenyl group is preferable. The bonding position of the alkenyl group is not particularly limited, and examples thereof include a molecular chain terminal, a molecular chain side chain, and both. Further, the content is preferably in the range of 0.001 to 3% by weight, more preferably 0.01 to 1% by weight in the component (a). The organic group bonded to the silicon atom other than the alkenyl group is usually an unsubstituted or halogen-substituted monovalent hydrocarbon group containing no aliphatic unsaturated bond. Specifically, alkyl groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl group; cycloalkyl groups such as cyclohexyl group and cycloheptyl group; phenyl group Aryl groups having 6 to 12 carbon atoms, such as benzyl, tolyl and xylyl groups; aralkyl groups having 7 to 20 carbon atoms, such as benzyl and phenethyl; 3,3,3-trifluoropropyl and chloromethyl And a halogenated alkyl group having 1 to 20 carbon atoms. Among these, it is preferable to select the component (a) so that the glass transition point or melting point thereof is lower than room temperature and becomes an elastomer at room temperature, and a methyl group is generally used. In particular, at least 85 mol% of the organic groups other than the alkenyl groups are preferably methyl groups, and more preferably at least 90 mol% are methyl groups. The molecular structure of the component (a) may be a straight chain or a partially branched straight chain, but is preferably a straight chain. The organopolysiloxane has a molecular weight such that the Williams plasticity measured by the method specified in the American Society for Testing and Materials (ASTM) D926 is 30 or more. That is, the plasticity number is a value obtained by multiplying the thickness (mm) of the test sample by 100 after holding the cylindrical test sample having a volume of 2 cm ^{2 and a} height of 10 mm under a compressive load of 49 Newton at 25 ° C. for 3 minutes. . This is because if the Williams plasticity of this component is less than 30, the (B) layer tends to be non-uniform. The upper limit of the plasticity is not particularly limited, but is preferably in a range that can be processed by a general mixing device. Specifically, it is preferably in the range of 30 to 200, more preferably in the range of 100 to 200, and still more preferably in the range of 120 to 185. Such a component (a) is preferably a high-consistency or raw rubber-like diorganopolysiloxane.

  Specific examples of the component (a) include dimethylsiloxane-methylvinylsiloxane copolymers with terminal trimethylsiloxy groups, methylphenylsiloxane-dimethylsiloxane / methylvinylsiloxane copolymers with terminal trimethylsiloxy groups, and diphenylsiloxane-dimethylsiloxane with terminal trimethylsiloxy groups.・ Methylvinylsiloxane copolymer, dimethylvinylsiloxane terminated with dimethylvinylsiloxy group, dimethylsiloxane blocked with dimethylvinylsiloxy terminal ・ Methylvinylsiloxane copolymer, methylphenylpolysiloxane blocked with dimethylvinylsiloxy terminal, methylphenylsiloxane blocked with dimethylvinylsiloxy terminal・ Dimethylsiloxane ・ Methylvinylsiloxane copolymer, terminal dimethylvinylsiloxy group Chain diphenylsiloxane-dimethylsiloxane-methylvinylsiloxane copolymers. In the above siloxane polymer, a siloxane polymer in which at least one terminal is a dimethylhydroxysiloxy group can be used. In these copolymers, the content of dimethylsiloxane units is preferably at least 90 mol%. Among them, dimethylpolysiloxane having a terminal dimethylvinylsiloxy group blocked and dimethylsiloxane / methylvinylsiloxane copolymer having a terminal dimethylvinylsiloxy group blocked are preferred. Also, methylphenylsiloxane / dimethylsiloxane / methylvinylsiloxane copolymer and diphenylsiloxane / dimethylsiloxane / methylvinylsiloxane copolymer are suitable for low-temperature use. As the component (a), such a siloxane polymer may be used alone or in a mixture of two or more.

  Methods for producing high-consistency alkenyl-containing polydiorganosiloxanes are well known, for example, by equilibrating a cyclic or linear dimethylsiloxane oligomer and a cyclic or linear methylalkenylsiloxane oligomer in the presence of a basic catalyst. It can be produced by reacting.

The component (b) is a crosslinking agent (curing agent) of the component (a), and is preferably an organohydrogenpolysiloxane having at least two hydrogen atoms bonded to silicon atoms. In this organohydrogenpolysiloxane, the content of silicon-bonded hydrogen atoms is preferably 0.2 to 2% by weight, more preferably 0.5 to 1.7% by weight. The position of the silicon-bonded hydrogen atom is not limited, and includes the end of the molecular chain, the side chain, and both. Examples of the organic group bonded to a silicon atom other than a hydrogen atom include the monovalent hydrocarbon groups exemplified for the component (a). Among them, an alkyl group, a phenyl group or a trifluoropropyl group is preferable, and a methyl group is particularly preferable. The molecular structure is not particularly limited, and includes a straight-chain, partially branched straight-chain, branched-chain, cyclic, and network-like structure, and is preferably a straight-chain homopolymer or copolymer. The component (b) preferably has compatibility with the component (a), and particularly when the component (a) has a high consistency or raw rubber, it is preferable that the component can be dissolved. The viscosity at 25 ° C. is preferably in the range of 0.5 to 1000 mPa · s, more preferably 2 to 500 mPa · s. Examples of such an organohydrogenpolysiloxane include a methylhydrogenpolysiloxane having a terminal trimethylsiloxy group, a dimethylsiloxane / methylhydrogensiloxane copolymer having a terminal trimethylsiloxy group, a dimethylpolysiloxane having a terminal dimethylhydrogensiloxy group, Gensiloxy group-blocked methyl hydrogen polysiloxane, terminal dimethyl hydrogen siloxy group-blocked dimethyl siloxane / methyl hydrogen siloxane copolymer, cyclic methyl hydrogen polysiloxane, cyclic dimethyl siloxane / methyl hydrogen siloxane copolymer, Si (OSiMe ₂ H) ₄ , PhSi (OSiMe ₂ H) ₃ low molecular weight such as a siloxane, and (CH _{3) 2} HSiO _1/2 units ( H _{3) 3} silicone resin composed of SiO _1/2 units and SiO _4/2 units, (CH _{3) 2} HSiO _1/2 units and (CH _{3) 3} SiO _1/2 units and CH ₃ SiO _3/2 A silicone resin composed of a unit, PhSiO _3/2 unit and SiO _4/2 unit is exemplified. In the formula, Me is a methyl group, and Ph is a phenyl group. Among them, methyl hydrogen polysiloxane or methyl hydrogen siloxane / dimethyl siloxane copolymer whose terminal is blocked by a trimethylsiloxy group or a dimethylhydrogensiloxy group is preferable. Many of these organohydrogenpolysiloxanes are commercially available. As the component (b), one of the above-mentioned siloxanes may be used alone, or two or more may be used in combination. The compounding amount of the component (b) is preferably such that the molar ratio of the silicon-bonded hydrogen atom in the present component to the alkenyl group in the component (a) is 1 to 50, and preferably 3 to 20. And more preferably 6 to 12.

  The component (c) is a catalyst for accelerating the curing of the silicone rubber composition. Specifically, platinum black, platinum supported on silica, platinum supported on carbon, chloroplatinic acid, an alcohol solution of chloroplatinic acid, platinum dichloride, platinum tetrachloride, platinum / olefin complex, platinum / alkenylsiloxane complex, platinum / beta- Platinum-based catalysts such as diketone complexes and platinum / phosphine complexes; rhodium-based catalysts such as rhodium chloride and rhodium chloride / di (n-butyl) sulfide complex; palladium-based catalysts such as palladium on carbon and palladium chloride Is exemplified. Among these, platinum-based catalysts are preferred. As the platinum / alkenylsiloxane complex, a complex obtained by reacting chloroplatinic acid with divinyltetramethyldisiloxane diluted with dimethylsiloxane having a dimethylvinylsiloxy group-terminated dimethylsiloxane (US Pat. No. 3,419,593) and neutralized complexes of platinum (IV) chloride with divinyltetramethyldisiloxane (see US Pat. No. 5,175,325). The added amount of the component (c) may be an amount sufficient to promote the reaction between the component (a) and the component (b) for curing. When a platinum-based catalyst is used, the amount of the platinum metal is preferably in the range of 0.1 to 500 ppm (weight) of the silicone-modified thermoplastic elastomer, more preferably 0.25 to 50 ppm (weight). .

The component (d) is a reinforcing filler and has an effect of reinforcing the silicone rubber formed by curing. Specifically, the specific surface area is preferably fumed silica ranging from 50 to 450 ² / g, more preferably fumed silica 50 to 400 m ² / g, more preferably fumed silica 200~380m ² / g. The surface of the component (d) is preferably subjected to a hydrophobic treatment. Examples of the hydrophobic method include a method in which a fumed silica is reacted with a liquid organosilicon compound having a silanol group. In addition, compounds referred to as an anti-crepe agent or a plasticizer in the silicone rubber field can be used as the surface treatment agent of the component (d). Examples of such compounds include polydiorganosiloxanes having a low molecular weight and having a hydroxy-terminated hydroxy group, polydiorganosiloxanes having a blocked alkoxy group, hexaorganodisiloxanes, cyclodimethylsilazanes, and hexaorganodisilazanes. Among them, a terminal organo group-blocked diorganopolysiloxane having an average degree of polymerization of 2 to 100 is preferable, and a terminal hydroxy group-blocked diorganosiloxane oligomer having an average degree of polymerization of 2 to 10 is more preferable. For example, when the component (a) is a polydimethylsiloxane having a vinyl group or a polydimethylsiloxane having a hexenyl group, it is preferable to use a polydimethylsiloxane having a terminal hydroxy group blocked as a surface treatment agent. The use amount of the surface treatment agent is preferably in the range of 5 to 50 parts by weight based on 100 parts by weight of the fumed silica. The amount of the component (d) is preferably in the range of 1 to 200 parts by weight, more preferably in the range of 5 to 150 parts by weight, and still more preferably in the range of 20 to 100 parts by weight, per 100 parts by weight of the component (a). .

  In the silicone-modified thermoplastic elastomer of the layer (B), the content of the silicone rubber composition is preferably at least 20% by weight, more preferably from 30 to 90% by weight, further preferably from 40 to 80% by weight. preferable. The layer (B) is obtained by dynamically vulcanizing a silicone rubber composition in a thermoplastic resin or a thermoplastic elastomer, and simultaneously with vulcanization of the rubber, an interface between the rubber and the thermoplastic resin or the thermoplastic elastomer. But the reaction proceeds. The vulcanized product of the silicone rubber composition is usually finely dispersed in a thermoplastic resin or a thermoplastic elastomer, and a part thereof may be reacted.

  The layer (B) contains an unsaturated ethylene group, an epoxy group, an amino group, an acid anhydride group, a silanol group, a carboxyl group, an alcohol for improving the dispersibility of the silicone rubber composition and improving the mechanical strength. Silane compounds having a hydroxyl group, a phenol group, an alkoxy group, an oisazoline group, etc .; a polydiamine having an epoxy group, an amino group, an acid anhydride group, a silanol group, a carboxyl group, an alcoholic hydroxyl group, a phenol group, an alkoxy group, an oisazoline group, etc. Organopolysiloxane; polydiorganosiloxane-polyamide copolymer, polydiorganosiloxane-polyester copolymer, polydiorganosiloxane-polyurethane copolymer, polydiorganosiloxane-polycarbonate copolymer, polydiorganosiloxane-polyurea copolymer, polydiorgane Siloxane - copolymers of polyacrylate copolymer may be added. These compounds are preferably used in an amount of 0.1 to 5 parts by weight for the silane compound, preferably 0.1 to 10 parts by weight for the polydiorganopolysiloxane, and 100 to 100 parts by weight of the thermoplastic resin or the thermoplastic elastomer. 0.1 to 10 parts by weight is preferred. Further, the layer (B) may contain various additives and fillers. As additives, for example, lubricants, strength improvers, antioxidants, ultraviolet absorbers, light stabilizers, heat stabilizers, plasticizers, foaming agents, crystal nucleating agents, antistatic agents, conductivity imparting agents, pigments and Examples include coloring agents such as dyes, cross-linking agents, flame retardants, fungicides, low-shrinkage agents, thickeners, release agents, anti-fogging agents, and bluing agents. Examples of the filler include glass fiber, carbon fiber, glass cloth, calcium carbonate, mica, talc, precipitated silica, silica aerogel, and ultrafine heat stable mineral materials such as titanium dioxide.

  The silicone-modified thermoplastic elastomer of the layer (B) is prepared, for example, by blending a silicone rubber composition, particularly the above components (a) to (d), in a thermoplastic resin or a thermoplastic elastomer melted by heating. It is obtained by vulcanization. Although the mixing order is not particularly limited, after a component (a) and a component (d) are previously mixed to prepare a silicone rubber base, this is dispersed in a thermoplastic resin or a thermoplastic elastomer, and then the component (b) And a method of adding components (c) and vulcanizing, or a method of mixing a mixture of components (a) to (d) with a thermoplastic resin or a thermoplastic elastomer and then vulcanizing the mixture. The components (a), (b) and (d) before vulcanization must be sufficiently dispersed in a thermoplastic resin or a thermoplastic elastomer. The mixing device may be any device that can uniformly disperse the above components in a thermoplastic resin or a thermoplastic elastomer, and examples thereof include a closed mixer and a twin screw extruder. The latter twin screw extruder is suitable for industrial production. The mixing temperature and mixing time vary depending on the type of the thermoplastic resin or the thermoplastic elastomer and the composition of the silicone rubber composition and are not particularly limited, but are set to a temperature at which the thermoplastic resin or the thermoplastic elastomer is sufficiently melted and does not decompose. It is preferred that the silicone rubber composition be quickly vulcanized while being heated and held. Specifically, it is preferable to carry out mixing and vulcanization at a temperature of 100 to 350 ° C. within 60 minutes, more preferably at 150 to 300 ° C. within 30 minutes. Such a silicone-modified thermoplastic elastomer is characterized in that it is replasticized by heating even after molding, so that a molded article having substantially the same physical properties can be obtained.

Next, a method for producing the composite of the present invention will be described.
The method for producing the composite of the present invention is not particularly limited, and a "comolding" method in which a thermoplastic resin or a thermoplastic elastomer and a silicone-modified thermoplastic elastomer are simultaneously melted and integrally molded, or a thermoplastic resin or a thermoplastic resin. An "overmolding" method is used in which one of the elastomer and the silicone-modified thermoplastic elastomer is heated and melted and molded, and then the other is heat-melted and molded on the surface. Examples of the molding method include injection molding, extrusion molding, and compression molding. In addition, a method of separately heating and melting a thermoplastic resin or a thermoplastic elastomer and a silicone-modified thermoplastic elastomer to form two molded articles, and applying an adhesive or a primer to the surface thereof and bonding them, And a method of heating the vicinity of the contact surface of the molded article to fuse it. Among these, the "comolding" method and the "overmolding" method are preferable from the viewpoint of workability.

The composite of the present invention as described above has excellent heat resistance, and also has characteristics of being excellent in recyclability because it can be plasticized again when heated after molding and can be molded again. Furthermore, the composite of the present invention has the advantage of having good mechanical strength. Therefore, the composite of the present invention includes various hoses and tubes such as brake hoses, fuel hoses and water hoses; cable coating materials such as control cables and high tension cords; sealing parts such as connectors and grommets; ducts such as air ducts. Classes; Boots such as CVJ boots, rack & pinion boots, MacPherson strut covers, steering rod covers, etc .; O-rings, packings, water pump packings, timing belt cover seals, oil pan seals, engine head cover packings, engine head cover mounts, gaskets, etc. Belts such as timing belts or their covering materials; leaf spring bushing, door latch striker, safety belt ratchet, window glass steady rest roll, absorber roll, ball jig Bush and anti-vibration parts such as intritainers; Caps; Interior materials such as handles, grips, trims, console boxes, instrument panels and seats; Interior parts of automobiles such as weather strips such as glass run channels, door seals and trunk seals; It can be used as a material for exterior parts and parts around the engine. In addition, coating materials such as electric cables, optical cables, wires, cords, and ropes; sealing materials such as window seals and gaskets; construction and construction materials such as sheet materials such as waterproof sheets and plastic flooring; cables and cords. Suitable for coating materials such as printer ink hoses, and electric and electronic parts materials such as hoses and tubes such as washing machine water absorption / drainage tubes. Other general uses include materials for tools such as handles and soft grips, and sports goods such as balls and shoes.
In addition, among the manufacturing methods of the present invention, the co-molding method and the over-molding method have a feature of being excellent in productivity and workability because the operation of incorporating a sealing material can be omitted. Further, according to the production method of the present invention, there is an advantage that a composite having excellent adhesion of each layer can be obtained without using an adhesive or a primer.

  When the composite of the present invention is applied to a hose, the inner layer and the outer layer are not particularly limited. In the case of a brake hose or a fuel hose, the inner layer is the (A) layer and the outer layer is the (B) layer. Is preferred.

  When the composite of the present invention is used as a connector, it is preferable that the housing part (hard part) is the (A) layer and the sealing part (elastic body part) is the (B) layer. The connector according to the present invention is a joint component such as an automobile, a general industrial machine, an electric / electronic device, and an electric wiring for construction / construction, and has an action of integrating and fixing the wiring and protecting an electronic contact at a joint. In particular, when used in applications exposed to the outdoors, such as automobiles and buildings and construction, waterproofness is important in terms of protecting electronic contacts. In such a connector of the present invention, after integrally molding one of the (A) layer and the (B) layer, an integrally molded product can be obtained on the surface of the molded product by an overmolding method of injection molding the other. it can.

  When the composite of the present invention is used as a sheet, the surface layer material is preferably the (B) layer, and the lower substrate is preferably the (A) layer. The thickness of the base material may be any thickness as long as the sheet can maintain sufficient strength, and specifically, is preferably in the range of 0.01 to 1 cm, more preferably 0.05 to 0.5 cm. The thickness of the surface layer material varies depending on the application and is not particularly limited, but is preferably in the range of 0.01 to 1 cm, more preferably 0.05 to 0.5 cm.

[Example]
Hereinafter, the present invention will be described in detail with reference to examples. In the examples, “parts” means “parts by weight”, and the viscosity is a value measured at 25 ° C. The raw materials used in the examples are as follows. Here, the PBT resin represents a polybutylene terephthalate resin, the TPU elastomer represents a thermoplastic polyurethane elastomer, Me represents a methyl group, and Vi represents a vinyl group.
○ Raw material nylon 6 resin-1: reagent manufactured by Alidrich Chemical Co., melting point 228.5 ° C
Nylon 6 resin-2: Amilan, CM1017, manufactured by Toray Industries, Inc.
PBT resin-1: reagent manufactured by Alidrich Chemical Co., melting point 227 ° C
PBT resin-2: manufactured by Toray Industries, Inc., trade name: Toray PBT resin, 1400X04
TPU elastomer-1: manufactured by Dow, trade name Pelletane, 2355-75A
TPU elastomer-2: manufactured by BASF Polyurethane Elastomers Co., Ltd., trade name: Elastolane, C80A
Thermoplastic Elastomer-1: manufactured by Toray DuPont, trade name Hytrel, 6347 (copolymer elastomer of PBT resin and polyether)
Thermoplastic Elastomer-2: AES Japan K.K., trade name Santoprene, 201-64 (an elastomer obtained by dynamically vulcanizing an ethylene-propylene-diene copolymer rubber in polypropylene)
Antioxidant: manufactured by Nippon Ciba Geigy, trade name Irganox 1010
Silicone rubber base: Diorganopolysiloxane raw rubber (containing a vinyl group) having a plasticity of 150 and comprising 99.67% by weight of Me ₂ SiO unit, 0.16% by weight of MeViSiO unit, and 0.17% by weight of Me ₂ ViSiO _1/2 unit. Amount: 0.10%) 68.8% by weight, fumed silica having a specific surface area of 250 m ² / g (manufactured by Cabot; trade name: Cab-O-Sil MS-75) 25.8% by weight, terminal having an average degree of polymerization of 4 hydroxy group-blocked dimethylpolysiloxane 5.4 wt%, consisting of ammonium carbonate 0.02 wt% silicone rubber base crosslinking agent: MeHSiO units 65.7 _wt%, Me 2 SiO units 32.4% by weight and _Me 3 SiO _{1 /} viscosity 30 mm ² / s consisting of ₂ units 1.9 wt% methyl hydrogen polysiloxane (silicon-bonded water Atom content 1.1%)
Platinum catalyst: 1.5% by weight of 1,3-divinyl-1,1,3,3-tetramethyldisiloxane platinum complex, 5.0% by weight of tetramethyldivinyldisiloxane, polydimethylsiloxane having a terminal dimethylvinylsiloxy group blocked Liquid mixture consisting of 93% and 0.5% by weight of dimethylcyclopolysiloxane having a degree of polymerization of 6 to 10

The tensile strength at break, elongation at break, JIS hardness and rebound resilience were measured according to the following methods.
-Tensile breaking strength The tensile breaking strength was measured according to the method specified in the plastic tensile test method (JIS-K7113-1995). As the test piece, a No. 2 type test piece was used.
-Elongation at break Tensile elongation at break was measured according to the method specified in JIS-K7113 "Method for tensile test of plastic" (1995). As the test piece, a No. 2 type test piece was used.
-JIS hardness It measured according to the method prescribed | regulated to JIS-K7215 "Durometer hardness test method of plastic" (1995). The thickness of the test piece was 6 mm.
-Rebound resilience It measured according to the method prescribed | regulated to JIS-K6255 "Rebound resilience test method of vulcanized rubber and thermoplastic rubber" (1996). The test method was a Lupke method, and the thickness of the test piece was 12.5 mm.

[Reference Example 1]
40 parts by weight of nylon 6 resin-1 and 0.5 parts by weight of an antioxidant were charged into a 250 mL Labo Plastomill (manufactured by Toyo Seiki Seisakusho) with a Banbury blade, and heated at 100 rpm under a temperature condition of 240 to 260 ° C. Heated and kneaded for minutes. Next, 60 parts by weight of the silicone rubber base was charged and heated and kneaded for 5 minutes in the same manner, and then 1.9 parts by weight of a crosslinking agent was added and kneaded for 5 minutes in the same manner. Finally, 1 part by weight of a 5% by weight solution of dimethylpolysiloxane (trade name: Dow Corning 200; manufactured by Dow Corning Corporation, 1000 mPa · s) of a platinum-based catalyst capped with a terminal trimethylsiloxy group was added, and the mixture was similarly heated and kneaded for 5 minutes. The mixture was taken out of the mixer and cooled to obtain a pale yellowish white massive silicone-modified thermoplastic elastomer A.
A part of the obtained block of the thermoplastic elastomer A is heated at 240 to 260 ° C. using a hot press (PY-5E manufactured by Kodaira Seisakusho) and a cold press (Mini Test Press-10 manufactured by Toyo Seiki Seisakusho). It was compression molded. The tensile strength at break, elongation at break, JIS hardness, and rebound resilience were measured using the obtained test pieces. Table 1 shows the results.
The remainder of the lump of the thermoplastic elastomer A was plasticized again using a single screw extruder ("UT-25-T" manufactured by Plastics Engineering Laboratory Co., Ltd.) and extruded to obtain pellets.

[Reference Example 2]
40 parts by weight of PBT resin-1 and 0.5 parts by weight of an antioxidant are charged into a 250 mL Labo Plastomill (manufactured by Toyo Seiki Seisakusho) with a Banbury blade, and are heated at a temperature of 240 to 260 ° C. at 100 rpm for 3 minutes. The mixture was heated and kneaded. Next, 60 parts by weight of the silicone rubber base was charged and heated and kneaded for 5 minutes in the same manner, and then 1.9 parts by weight of a crosslinking agent was added and kneaded for 5 minutes in the same manner. Finally, 1 part by weight of a 5% by weight solution of dimethylpolysiloxane (trade name: Dow Corning 200; manufactured by Dow Corning Corporation, 1000 mPa · s) of a platinum-based catalyst capped with a terminal trimethylsiloxy group was added, and the mixture was similarly heated and kneaded for 5 minutes. This mixture was taken out of the mixer and cooled to obtain a silicone-modified thermoplastic elastomer B as a pale yellowish white block.
A part of the obtained block of the thermoplastic elastomer B is heated at 240 to 260 ° C. using a hot press (PY-5E, manufactured by Kodaira Seisakusho) and a cold press (Mini Test Press-10, manufactured by Toyo Seiki Seisakusho). It was compression molded. The tensile strength at break, elongation at break, JIS hardness, and rebound resilience were measured using the obtained test pieces. Table 1 shows the results.
The remainder of the mass of the thermoplastic elastomer B was again plasticized and extruded using a single screw extruder (“UT-25-T” manufactured by Plastics Engineering Laboratory Co., Ltd.) to obtain pellets.

[Reference Example 3]
50 parts by weight of TPU elastomer-1 and 0.5 parts by weight of an antioxidant are charged into a 250 mL Labo Plastomill (manufactured by Toyo Seiki Seisakusho) with a Banbury blade, and are heated at 100 to 3 minutes at a temperature of 180 to 200 ° C. for 3 minutes. The mixture was heated and kneaded. Next, 50 parts by weight of a silicone rubber base was blended and heated and kneaded for 5 minutes in the same manner. Then, 1.6 parts by weight of a crosslinking agent was added and heated and kneaded for 5 minutes in the same manner. Finally, 1 part by weight of a 5% by weight solution of a dimethylpolysiloxane (trade name: Dow Corning 200; manufactured by Dow Corning Corporation, 1000 mPa · s) of a platinum-based catalyst capped with a terminal trimethylsiloxy group was added, and the mixture was similarly heated and kneaded for 5 minutes. The mixture was taken out of the mixer and cooled to obtain a pale yellowish white blocky silicone-modified thermoplastic elastomer C.
A part of the obtained mass of the thermoplastic elastomer C is heated at 180 to 200 ° C. using a hot press (PY-5E, manufactured by Kodaira Seisakusho) and a cold press (Mini Test Press-10, manufactured by Toyo Seiki Seisakusho). It was compression molded. The tensile strength at break, elongation at break, JIS hardness, and rebound resilience were measured using the obtained test pieces. Table 1 shows the results.
The remainder of the mass of the thermoplastic elastomer C was plasticized again using a single screw extruder (“UT-25-T” manufactured by Plastics Engineering Laboratory Co., Ltd.) and extruded to obtain pellets.

[Table 1]

  Using a small-sized manual injection molding machine (model CS-183MMX, manufactured by CSI), the thermoplastic resin or thermoplastic elastomer pellets shown in Table 2 were injection-molded to a length of 32 mm, a width of 12 mm and a thickness of 3 mm. A plate-shaped molded piece (base material layer) was formed. The molding temperature was selected in the range of 200 ° C. to 260 ° C. according to the type of the thermoplastic resin or the thermoplastic elastomer. Next, the obtained molded piece was transferred to another mold, and the silicone-modified thermoplastic elastomers A to A obtained in Reference Examples 1 to 3 were placed thereon so that the contact surface became 10 mm long × 12 mm wide. The pellets of C (overmold layer) were injection molded to obtain test pieces (composites 1 to 5) for measuring adhesive strength shown in FIG.

  Both ends (non-contact surfaces) of the composites 1 to 5 thus obtained were pulled at an angle of 180 degrees using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph, M50), and the adhesive strength (up to breaking) was obtained. Was measured. The tensile speed at this time was 20 mm / min for the composites 1 and 3, and 100 mm / min for the composites 2, 4, and 5. Moreover, the state of the fractured surface after the measurement was visually observed. The results are shown in Table 2. From these results, it was found that in the composite 4, the base layer and the overmold layer were extremely tightly adhered. On the other hand, materials such as composites 1, 2, 3, and 5 in which the base material layer and the overmold layer are in good contact with each other and can be separated cleanly at the time of peeling have the advantage that they can be separated and recycled. I have.

  Furthermore, after the molded pieces A to C of the peeled silicone-modified thermoplastic elastomer are finely cut with scissors, they are re-melted using a small-sized manual injection molding machine (model CS-183MMX manufactured by CSI) and injection molded. A small dumbbell having a thickness of 2 mm was formed. The molding temperature was selected in the range of 200 ° C. to 260 ° C. according to the type of the thermoplastic elastomer. The tensile breaking strength of the obtained small dumbbell was measured. Table 3 shows the results. Table 3 also shows the tensile strength at break and recyclability measured in Reference Examples 1 to 3.

[Comparative Example 1]
In the same manner as in Example 1, pellets of PBT resin-2 were injection molded to form plate-shaped molded pieces. Next, when a pellet of the thermoplastic elastomer-1 was injection-molded thereon, it did not adhere sufficiently to the substrate layer, and a composite composed of the substrate layer and the overmold layer was not obtained.

[Table 2]

[Table 3]

  Using a small-sized manual injection molding machine (model CS-183MMX manufactured by CSI), pellets of the thermoplastic resin or the thermoplastic elastomer shown in Table 4 were injection-molded, and a length of 32 mm × a width of 12 mm × a thickness of 3 mm was obtained. A plate-shaped molded piece (base material layer) was formed. The molding temperature was selected in the range of 200 ° C. to 260 ° C. according to the type of the thermoplastic resin or the thermoplastic elastomer. Next, the obtained molded piece was transferred to another mold, heated to a temperature equal to or higher than the melting point or softening point, and re-melted. On this, the contact surface was 10 mm in length × 12 mm in width. Pellets of the silicone-modified thermoplastic elastomers A to C (co-mold layers) obtained in 1 to 3 were injected and integrally molded to obtain test pieces (composites 6 to 8) for measuring adhesive strength shown in FIG. .

  Both ends (non-contact surfaces) of the composites 6 to 8 thus obtained were pulled at an angle of 180 ° using a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Strograph, M50), and the adhesive strength (up to breaking) was obtained. Was measured. The tensile speed at this time was 20 mm / min for the composites 6 and 7, and 100 mm / min for the composite 8. Further, the state of the fracture surface after the measurement was visually observed. Table 4 shows the results.

  Furthermore, the exfoliated molded pieces A to C of the silicone-modified thermoplastic elastomer were injection-molded using an injection molding machine (SS-15-15, manufactured by Yamashiro Seisakusho) to obtain a JIS-2 dumbbell (K7113-1981). Molded. The molding temperature was selected in the range of 200 ° C. to 260 ° C. according to the type of the silicone-modified thermoplastic elastomer. The tensile breaking strength of the JIS-2 dumbbell molded piece was measured using a tensile tester (RTC-1325A, manufactured by Orientec). Further, the dumbbell molded piece obtained above was suspended in two hot-air circulating ovens (manufactured by Yamato; DH-41, manufactured by Tavai Spec; PH300) set at 157 ° C. and 180 ° C. After taking out and cooling after a predetermined time, the tensile strength at break was measured in the same manner as above. From these measured values, the heat resistance was calculated according to the following equation. Table 5 shows the results. Table 5 also shows the heat resistance of the thermoplastic elastomer-1 and the thermoplastic elastomer-2 measured in the same manner as described above.

Further, the molded pieces A to C of the peeled silicone-modified thermoplastic elastomer were subjected to hot pressing (PY-5E, manufactured by Kodaira Seisakusho) and cold press (Mini Test Press-10, manufactured by Toyo Seiki Seisakusho) to a thickness of 1 mm. It was molded into a flat molded piece of 0.6 mm. After 200 g of toluene or ion-exchanged water was charged into a 450 cc glass round bottle, the mouth of the glass round bottle was covered with a plate-shaped piece of the silicone-modified thermoplastic elastomer using a fixing jig. Here, the area of the opening of the glass round bottle was 28.3 cm ² . After leaving this glass round bottle at 23 ° C. for 10 days, toluene or ion-exchanged water in the bottle was taken out and its weight was measured. From the results, the permeability (%) of toluene and water vapor was calculated according to the following equation. The results are shown in Table 6. Table 6 shows the permeation of the thermoplastic elastomer-1 and a sheet of silicone rubber (manufactured by Dow Corning Toray Silicone, trade name: DY32-4106) (thickness: 1.6 mm) measured in the same manner as described above. The gender is also described. From these results, it has been found that the silicone-modified thermoplastic elastomers A to C have excellent barrier properties against toluene and water, despite having a high concentration of silicone rubber of 50% by weight or more.

[Comparative Example 2]
In the same manner as in Example 2, pellets of PBT resin-2 (base material layer) are injection-molded to form a plate-shaped molded piece, which is then heated and re-melted, and a thermoplastic elastomer-1 (co-mold layer) is formed thereon. Was injected and molded integrally to obtain a composite 9. The adhesive strength of the obtained composite was measured at a tensile speed of 20 mm / min in the same manner as in Example 2. Further, the state of the fracture surface after the measurement was visually observed. Table 4 shows the results.

[Table 4]

[Table 5]

[Table 6]

  Nylon 6 resin-2 and silicone-modified thermoplastic elastomer A were co-extruded using a single-screw extruder ("UT-25-T" manufactured by Plastics Engineering Laboratory Co., Ltd.) to obtain a two-layer structure shown in FIG. Got a hose. The diameter of this hose was 10 mm, the inner layer was nylon 6 resin-2 having a thickness of 1 mm, and the outer layer was silicone-modified thermoplastic elastomer A having a thickness of 1 mm. The molding temperature was 240 ° C to 260 ° C. When the tactile sensation of the obtained hose was measured, it had both a stiffness and a soft feeling on the surface, and was very good. Further, when the adhesion state between the two layers was confirmed by hand, both layers were firmly adhered.

  Using an injection molding machine (SS-15, manufactured by Yamashiro Seisakusho), a cylindrical molded piece of nylon 6 resin-1 having a diameter of 10 mm, a height of 5 mm, and a thickness of 1 mm was prepared. The molding temperature at this time was 240 ° C to 260 ° C. Next, after inserting a cylindrical mold having a diameter of 1.0 mm into the inner central portion of the cylindrical molded piece, a silicone-modified thermoplastic elastomer B is injection-molded between the mold and the nylon 6 resin-1. A connector having a hole having a diameter of 1.0 mm at the center shown in FIG. 3 was obtained. The molding temperature at this time was 180 to 200 ° C. When the tactile sensation of the obtained connector was measured, it had both a stiffness sensation and a soft sensation on the surface, and was very good. Further, when the adhesion state between the two layers was confirmed by hand, they were firmly adhered. Furthermore, an electric wire having a diameter of 1.2 mm was inserted into a hole at the center of the inner layer, and the adhesion was checked by hand. As a result, the inner layer of the connector and the electric wire were in good contact.

  Using a hot press (PY-5E manufactured by Kodaira Seisakusho) and a cold press (Mini Test Press-10 manufactured by Toyo Seiki Seisakusho), a 2 mm thick sheet made of TPU elastomer-2 was prepared. Further, a silicone-modified thermoplastic elastomer C was compression-molded on the sheet surface to form a surface layer having a thickness of 0.2 mm. The thus obtained sheet having a thickness of about 2.2 mm had very good surface slipperiness.

FIG. 1 is a perspective view of a test piece for measuring the adhesive strength of the composite of the present invention prepared in Example 1 and Example 2. FIG. 2 is a perspective view of the hose obtained in Example 3. FIG. 3 is a perspective view of the connector obtained in the fourth embodiment.

Explanation of reference numerals

DESCRIPTION OF SYMBOLS 1 Base material layer 2 Overmold layer or co-mold layer 3 Nylon 6 resin-2
4 Silicone-modified thermoplastic elastomer A
5 Nylon 6 resin-1
6. Silicone-modified thermoplastic elastomer B

Claims (9)

(A) a thermoplastic resin layer or a thermoplastic elastomer layer,
(B) A composite comprising a silicone-modified thermoplastic elastomer layer obtained by vulcanizing a silicone rubber composition in a thermoplastic resin or a thermoplastic elastomer. (B) The thermoplastic resin or the thermoplastic elastomer in the layer is composed of a polyester resin, a polyamide resin, a polyolefin resin, a thermoplastic polyurethane elastomer, a thermoplastic polyester elastomer, a thermoplastic polyamide elastomer, and a thermoplastic polyolefin elastomer. The composite according to claim 1, wherein the silicone rubber composition is an addition-curable silicone rubber composition selected from the group. (B) The silicone rubber composition in the layer is
(A) an organopolysiloxane having at least two alkenyl groups in one molecule and having a Williams plasticity of at least 30;
(B) an organosilicon compound having at least two silicon-bonded hydrogen atoms in one molecule,
(C) a catalyst for a hydrosilylation reaction,
The composite according to claim 2, wherein (d) an addition reaction-curable silicone rubber composition containing fumed silica as a main component. (A) The layer is selected from a polyamide resin, a polyester resin, a polycarbonate resin, a styrene-based vinyl resin, a polyolefin-based resin, a thermoplastic polyurethane-based elastomer, a thermoplastic polyester-based elastomer, a thermoplastic polyamide-based elastomer, and a thermoplastic polyolefin-based elastomer. The composite according to claim 1, which is a thermoplastic resin layer or a thermoplastic elastomer layer. The composite according to claim 1, which is for a hose. The composite according to claim 1, which is for a connector. The composite according to claim 1, which is for a sheet. The method for producing a composite according to claim 1, wherein the thermoplastic resin or the thermoplastic elastomer and the silicone-modified thermoplastic elastomer are heated and melted and simultaneously molded. The method according to claim 1, characterized in that one of the thermoplastic resin or the thermoplastic elastomer and the silicone-modified thermoplastic elastomer is heated and melted and molded, and then the other surface is heated and melted to be molded. A method for producing the composite according to the above.

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