Bonding elastomers.

[Detailed Description of the Invention]

The background of an invention The present invention points to the improved method which pastes up the layer of both compounds on Mutually by mixing a polysulfide system silicon analogue before vulcanization in both a Fluoro elastomeric composition, and butadiene acrylonitrile polymer combination both [ one side or ] of a layer. Explanation of conventional technology Prior art is abundant about the composite material built by joining at least two layers of a different polymer material together. The improvement in joining these layers together was attained by introducing one adhesion layer between two-layer [ of different polymer ], as it was in the British patent application No. 2072576. Attaining good adhesion in other fluoride non-containing polymer combination things of a Fluoro elastomeric composition has been accepted as one difficult subject for a long time. Generalization of the present invention Before an applicant joins one layer of a butadiene acrylonitrile polymer combination thing here and vulcanizes one layer of a Fluoro elastomeric composition here, a polysulfide system silicon analogue is mixed in one side of these combination things, or both, The improved method on which both these layers are pasted up was discovered. Since the improved method which pastes up one layer of a Fluoro elastomeric composition on one layer of a butadiene acrylonitrile polymer combination thing is provided according to the present invention, it is Then, In this case, in a butadiene acrylonitrile polymer combination thing, that improvement mixes about 1 per 100 weight sections to about 5-weight section polysulfide system silicon analogue of butadiene acrylonitrile polymer, before joining both layers together, And it comprises vulcanizing these layers by a contact state mutually, and is Standing. According to the present invention, in a Fluoro elastomeric composition, about 1 per 100 weight sections to about 5-weight section polysulfide system silicon analogue of a Fluoro elastomeric composition is mixed, before joining the two above-mentioned layers together, And since both these layers are vulcanized in a mutual contact state, improvement changes and the adhesion corrective strategy of Standing and both the above-mentioned layers is provided. According to [ again ] the present invention, it is, It is about 1 per 100 weight sections each to about 3-weight section polysulfide system silicon analogue of a Fluoro elastomer and butadiene acrylonitrile polymer in [ each ] a Fluoro elastomeric composition and a butadiene acrylonitrile polymer combination thing. Since it mixes before joining both these layers together, and these layers are vulcanized in a mutual contact state, improvement changes and adhesion To corrective strategy is provided with the layer of Standing and a Fluoro elastomeric composition, and the layer of butadiene acrylonitrile polymer. According to the present invention, it consists of two-layer, a inner layer is a Fluoro elastomeric composition, an outer layer is a butadiene acrylonitrile polymer combination thing, and it is Then again, About 1 per 100 weight sections each to about 5-weight section polysulfide system silicon analogue of butadiene acrylonitrile polymer or a Fluoro elastomer is included in one of layers, A hose collection object is provided and this hose collection object is vulcanized by heating for about 10 minutes to about 60 minutes in the temperature of about 150degreeC to about 180 degreeC. Detailed description of an invention In the present invention, a useful Fluoro elastomer is polymer based on fluoridation Vinylidene and hexafluoropropylene, and contains ethylene-like unsaturated Ole Huynh arbitrarily with 4 fluoridation ethylene and other fluorination compounds like perfluoromethylvinylether. These polymer is built by the high-pressure-water emulsion polymerization which generally uses a fluorocarbon Floating-ized agent, a fault sulfate initiator, and a molecular weight regulation agent. If only a combination person adds a metal oxide acid acceptor, a bulking agent, and the arbitrary ingredient for combination, most of these polymer can be obtained with the mixed curing system so that a combination thing suitable for hardening may be generated. Each Fluoro elastomer and the exact character of the mixed curing system are not generally clarified. In the present invention, useful butadiene acrylonitrile is built by free radical water emulsion polymerization, and contains about 50 to about 80% of the weight of butadiene, and about 20 to about 50% of the weight of acrylonitrile. It is preferred to use about 30 to about 40% of the weight of acrylonitrile and the polymer which contains about 60 to about 70% of the weight of butadiene corresponding to it. Such polymer is known well commercially. The curing system by which Fluoro elastomer; mixture of the Fluoro elastomeric composition to be used was done; magnesium oxide, acid-acceptor; Many minerals reach from one or one like cadmium oxide, a calcium oxide, calcium hydroxide, and a zinc oxide, It may consist of many bulking agents; from one or one like carbon black, silica, and barite, and carnauba wax, low molecular weight polyethylene, and processing aid like Penta erythritol tetra-stearate may be included. Such a combination thing can be built with the mixing method of the common knowledge including roll machine mixture and direct vent type mixer mixture. The butadiene acrylonitrile polymer combination thing to be used, One or the bulking agent of many [ one ] like butadiene acrylonitrile polymer, carbon black, silica, and barite; it is dioctyl phthalate arbitrarily, Dibutyl phtalate, dioctyl adipate, dibutyl sebacate, and a compatibility plasticizer like dioctyl sebacate; magnesium oxide, It is much antioxidant; dicumyl peroxide from one which has much especially metal oxide; low volatility from one or one like cadmium oxide, a calcium oxide, and a zinc oxide, or one, The hardening auxiliary agent for using it together with organic peroxide like organic peroxide; like lauryl peroxide and benzoyl peroxide, phenylenedimaleimide and various kinds of G, or tree (meta) acrylate is comprised, and it is Standing. A little Fluoro elastomers may be mixed with butadiene acrylonitrile polymer again, and the quantity is quantity that a Fluoro elastomer does not form many Fluoroelastomer― butadiene acrylonitrile polymer mixing things from about 25 % of the weight. Such a combination thing can be built with the mixing method of the common knowledge including mixture in a roll on a plane or a sealing mixer. It is a Fluoro elastomeric composition in the present invention. Or the polysulfide system silicon analogue added to a butadiene acrylonitrile polymer combination thing can be chosen from Screw― [alkoxy silyl Alkyl] ―Tetra sulfide and Screw― [alkoxy silyl Aryl] ―Tetra sulfide. The examples of such a polysulfide system silicon analogue are Screw― [3-(triethoxy silyl) ―Propyl] ―Tetra sulfide and Screw― [triethoxy silyl ethyl Tolylene] ―Tetra sulfide. The amounts of addition of a polysulfide system silicon analogue are about 1 per 100 weight sections to about 5 of a Fluoro elastomer or butadiene acrylonitrile polymer weight sections, preferably about 1.5 to about 4 weight sections. When adding a polysulfide system silicon analogue to both a Fluoro elastomeric composition and a butadiene acrylonitrile polymer combination thing, About 1 per 100 weight sections to about 3-weight section polysulfide system Silang of a Fluoro elastomeric composition or a butadiene acrylonitrile polymer combination thing is added. A polysulfide system silicon analogue can be simultaneously added easily to a Fluoro elastomeric composition or butadiene acrylonitrile polymer, when adding other combination ingredients. It is I and It was to give the result which should generally [ it is preferred to add polysulfide system Silang only only to one combination thing, and / the addition to a butadiene acrylonitrile polymer combination thing ] be satisfied from an economic reason. A Fluoro elastomeric composition and a butadiene acrylonitrile polymer combination thing are fabricated by the sheet of suitable thickness, the surface of these sheets -- for example, either of the surface sanctification agents of common knowledge like cyclohexanone -- with, it wipes finely, and another side is established in piles in one top, a sheet is put in a model, and it vulcanizes by heating for about 10 minutes to about 60 minutes to the temperature of about 150degreeC to about 180 degreeC. The use of the complex which the present invention made stratified contains a fuel system hose, other hose for the transfer of various kinds of organic substances, inner tension of a container, a film, etc. which have a Fluoro elastomer in a inner layer. The hose can build an inner side core, is a group string or a spiral reinforcing material, with can cover this, and can be manufactured by a method so that according to vulcanizing the whole for one covering following Apply it and this arbitrarily. A core is the present invention and it can build it with one layered product which has two-layer, It is a Fluoro elastomeric composition, an outer layer is a butadiene acrylonitrile polymer combination thing, and a inner layer is Then, one of layers are the things containing polysulfide system Silang --; -- the next -- this core material -- the group string or spiral of suitable thread or a wire -- with -- strengthening by surrounding -- and this strengthened core -- arbitrary -- one covering -- Apply -- things are made. This whole collection object is vulcanized by heating next. In order to vulcanize a core material partially, it is the method that microwave energy is used, and it is also possible to use various kinds of methods of reducing a Netsuku down or flat-izing of a core material during processing. The following examples explain the present invention and all parts are with weight. Example 1 the combination table showing a Fluoro elastomeric composition and a butadiene acrylonitrile polymer combination thing in a The table -- therefore, Ivy attached by mixing by the roll on a plane of a two-piece roll for rubbers. By mixing with cyclohexanone, these layers of two combination things about 0.15 cm thick made the surface pure, pushed one side on another side in the model, and vulcanized it by heating by 160 degreeduring 45 minutes C. Thus, it measures using the Instron testing machine into which carry out peeling of the peel strength of the formed layered product, and it makes a layered product divide by a part for 30-cm/in speed, and the result is shown in the The table.

[Table]

[Table]

[Table]

Run The Front peel strength (kN/m) It is combination thing 1 to combination thing 3. 0.6 It is combination thing 1 to combination thing 4. 0.8 It is combination thing 2 to combination thing 3. 0.6 It is combination thing 2 to combination thing 4. The adhesive improvement to 1.5 combination thing 4 is found easily. Example 2 the combination table showing a butadiene acrylonitrile polymer combination thing in a The table -- therefore, Ivy to attach. Ivy which attaches a layered product by vulcanizing by pressing the sheet of these combination things to the sheet of combination thing No.2 of Example 1, and heating it for 45 minutes by 160 degreeC. The peel strength of these layered products is measured and a result is shown in a The table. In this, combination thing No.10 and 11 are contrast standards, and are outside the range of the present invention.

[Table]

Example 3 combination of combination thing No.2 of Example 1 -- therefore, Ivy which attaches a Fluoro elastomeric composition. combination of combination thing No.10 of Example 2 -- therefore, Ivy which attaches a combination thing by adding Silang to each as a butadiene acrylonitrile polymer combination thing is built and it is further shown in a The table. A layered product is built, vulcanized and examined like Example 1, and a result is shown in a The table. In this, only combination thing No.21 is within the limits of the present invention.

[Table]

Example 4 Building two Fluoro elastomeric compositions, the only difference is that a polysulfide system silicon analogue is contained in one of them. Building two butadiene acrylonitrile polymer combination things, the only difference is that a polysulfide system silicon analogue is contained in one of them. Combination is shown in a The table. Ivy which attaches a layered product by vulcanizing by pushing on up to each butadiene acrylonitrile polymer combination thing, and heating each Fluoro elastomer for 45 minutes by 160 degreeC continuously. Peel strength data is shown in a The table. The layered product made to form by pasting up combination thing No.31 on each of combination thing No.32 and 33, and pasting up combination thing No.33 on combination thing No.30 is within the limits of the present invention, The layered product formed by pasting up combination thing No.30 on combination thing No.32 on the other hand is outside the range of the present invention.

[Table]

[Table]

Example 5 A butadiene acrylonitrile polymer combination thing is built as shown in a The table, Silang 1 is Screw― [3-(triethoxy silyl) ―Propyl] ―Tetra sulfide in it, and Silang 2 is Screw― [triethoxy silyl ethyl Tolylene] ―Tetra sulfide. it is a statement to Example 1 -- like -- the layer of these combination things -- combination thing No.2 of Example 1 -- much more -- or the peel strength of the layered product which pressed on [ much more ] the by ton combination thing, stiffened by 160 degreeduring 30 minutes C, and was made to form in this way is measured, and a result is shown in a The table.

[Table]

The present invention includes the following embodiment. (1) a Fluoro elastomeric composition -- Fluoro elastomer; -- the mixed curing system; magnesium oxide, It is much inorganic acid acceptors; and carbon black from one or it which is chosen from cadmium oxide, a calcium oxide, calcium hydroxide, and a zinc oxide, A method given in the 1st paragraph of a claim characterized by the thing which is chosen from silica and barite, and which consist of many bulking agents; from it one again. (2) Butadiene acrylonitrile polymer in which a butadiene acrylonitrile polymer combination thing contains about 20 to about 50% of the weight of acrylonitrile; carbon black, one or it which is chosen from silica and barite -- many bulking agents; -- arbitrary -- compatibility plasticizer; magnesium oxide, A method given in the 1st paragraph of the above characterized by many of even metal oxides; comprising many antioxidant; organic peroxide; and hardenability auxiliary agents; from it from one or it which is chosen from cadmium oxide, a calcium oxide, and a zinc oxide. (3) A method given in the 1st paragraph of a claim vulcanizing by heating the layer of a Fluoro elastomeric composition, and the layer of the combination thing of butadiene acrylonitrile polymer for about 10 minutes to about 60 minutes to the temperature of about 150degreeC to about 180 degreeC. (4) A butadiene acrylonitrile polymer combination thing contains an organic peroxide hardening agent, vulcanizing by heating the layer of a butadiene acrylonitrile polymer combination thing, and the layer of a Fluoro elastomeric composition for about 10 minutes to about 60 minutes to the temperature of about 150degreeC to about 180 degreeC -- and A method given in the 3rd paragraph of a claim characterized by what a polysulfide silicon analogue is chosen for from Screw― [3-(triethoxy silyl) ―Propyl] ―Tetra sulfide and Screw― [triethoxy silyl ethyl Tolylene] ―Tetra sulfide. (5) Fluoro elastomeric compositions are a Fluoro elastomer and the mixed curing system, Magnesium oxide, cadmium oxide, a calcium oxide, calcium hydroxide, And it is an acid acceptor of many minerals from one or it which is chosen from a zinc oxide, And they are many bulking agents from one or it which is chosen from carbon black, silica, and barite, Consist of, butadiene acrylonitrile polymer in which a butadiene acrylonitrile polymer combination thing contains about 20 to about 50% of the weight of acrylonitrile, They are many bulking agents from one or it which is chosen from carbon black, silica, and barite, comprising many a metal oxide, organic peroxide, and hardenability auxiliary agents from one or it which is arbitrarily chosen from a compatibility plasticizer, magnesium oxide, cadmium oxide, a calcium oxide, and a zinc oxide -- and ; as which a polysulfide silicon analogue is chosen from Screw― [3-(triethoxy silyl) ―Propyl] ―Tetra sulfide and Screw― [triethoxy silyl ethyl Tolylene] ―Tetra sulfide -- a hose collection object given in the 4th paragraph of a claim characterized by things.