WO2014123037A1 - Corps stratifié - Google Patents

Corps stratifié Download PDF

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Publication number
WO2014123037A1
WO2014123037A1 PCT/JP2014/051851 JP2014051851W WO2014123037A1 WO 2014123037 A1 WO2014123037 A1 WO 2014123037A1 JP 2014051851 W JP2014051851 W JP 2014051851W WO 2014123037 A1 WO2014123037 A1 WO 2014123037A1
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WIPO (PCT)
Prior art keywords
fluororubber
layer
rubber
vulcanization
laminate
Prior art date
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PCT/JP2014/051851
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English (en)
Japanese (ja)
Inventor
充宏 大谷
昌興 金
Original Assignee
ダイキン工業株式会社
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Publication of WO2014123037A1 publication Critical patent/WO2014123037A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/042—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/16—Layered products comprising a layer of natural or synthetic rubber comprising polydienes homopolymers or poly-halodienes homopolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings

Definitions

  • the present invention relates to a laminate.
  • fluororubber Since fluorororubber exhibits excellent chemical resistance, solvent resistance, and heat resistance, it is widely used in various fields such as the automobile industry, semiconductor industry, and chemical industry. For example, in the automobile industry, they are used as hoses, sealing materials, etc. for engines and peripheral devices, AT devices, fuel systems and peripheral devices.
  • fluororubber exhibits the above-mentioned excellent characteristics, its price is very expensive compared to ordinary rubber materials, and it is a problem in terms of cost to make materials such as hoses using only fluororubber. There is. Therefore, it has been proposed to use fluororubber and non-fluororubber together.
  • ozone resistance is required for fuel hoses used in fuel systems in the automobile industry.
  • acrylonitrile butadiene rubber and polyvinyl chloride are used as the non-fluorine rubber. It has been proposed to use a mixture.
  • the adhesiveness to the fluoro rubber is lowered when the acrylonitrile butadiene rubber and polyvinyl chloride are mixed.
  • Patent Document 1 discloses that an inner layer using fluororubber and an outer layer vulcanized and bonded to the inner layer using a blend material of acrylonitrile-butadiene rubber and polyvinyl chloride.
  • a blended acrylonitrile in the acrylonitrile-butadiene rubber in the blend material wherein the blending amount of polyvinyl chloride in the blend material is 15 to 45 parts by weight in 100 parts by weight of the blend material 1,8-diazabicyclo- (5,4,0) -undecene-7 salt of carboxylic acid having a specific structure, the content of which is 28 to 42% by weight and the blend material and / or fluororubber
  • a fuel hose characterized in that is blended is described.
  • Patent Document 2 describes a crosslinkable composition comprising a fluororubber, a crosslinker, and a specific additive for the purpose of improving the adhesion between the fluororubber and the epichlorohydrin rubber.
  • the present invention provides a laminate in which a fluoro rubber layer made of fluoro rubber, an acrylonitrile butadiene rubber, and a non-fluoro rubber layer made of polyvinyl chloride are firmly bonded.
  • the present invention is a laminate comprising a non-fluorine rubber layer (A) and a fluorine rubber layer (B) laminated on the non-fluorine rubber layer (A), wherein the non-fluorine rubber layer (A) It is a layer formed from a rubber composition for vulcanization, and the rubber composition for vulcanization includes acrylonitrile butadiene rubber (a1-1), polyvinyl chloride (a1-2), and the following formula (1):
  • the fluororubber layer (B) containing (a2) is a laminate formed of a fluororubber composition containing the fluororubber (b1).
  • the rubber composition for vulcanization preferably further contains magnesium oxide.
  • the rubber composition for vulcanization preferably further contains an epoxy resin.
  • the fluororubber (b1) is preferably a vinylidene fluoride fluororubber or a tetrafluoroethylene / propylene fluororubber.
  • the fluororubber composition preferably further contains the compound (a2) represented by the formula (1).
  • the present invention also provides acrylonitrile butadiene rubber (a1-1), polyvinyl chloride (a1-2), and the following formula (1):
  • R 1 , R 2 and R 3 are the same or different and each represents a hydrogen atom or a monovalent organic group having 1 to 30 carbon atoms, and X 1 is an anion
  • It is also a rubber composition for vulcanization characterized by containing (a2).
  • the laminate of the present invention has the above configuration, the fluororubber layer made of fluororubber, the non-fluororubber layer made of acrylonitrile butadiene rubber and polyvinyl chloride are firmly bonded.
  • the laminate of the present invention is a laminate comprising a non-fluorinated rubber layer (A) and a fluororubber layer (B) laminated on the non-fluorinated rubber layer (A).
  • A non-fluorinated rubber layer
  • B fluororubber layer laminated on the non-fluorinated rubber layer (A).
  • the fluorine rubber layer (B) containing (a2) is a layer formed from a fluorine rubber composition containing fluorine rubber (b1).
  • the rubber composition for vulcanization for forming the non-fluorine rubber layer (A) contains the compound (a2) represented by the above formula (1), whereby Even if it is a blend of vinyl chloride and acrylonitrile butadiene rubber, the non-fluororubber layer and the fluororubber layer can be firmly bonded.
  • the laminated body of this invention is excellent in ozone resistance. Furthermore, in the laminate of the present invention, when laminating the fluororubber layer and the non-fluororubber layer, a particularly strong adhesion can be obtained at the time of rubber vulcanization without a particularly complicated process. This process is unnecessary, and molding at low cost is possible and molding is also easy. Moreover, since it can shape
  • the laminate of the present invention comprises a non-fluororubber layer (A) and a fluororubber layer (B) laminated on the non-fluororubber layer (A).
  • Non-fluorinated rubber layer (A) Non-fluorinated rubber layer
  • the non-fluorinated rubber layer (A) is a layer formed from a rubber composition for vulcanization.
  • the rubber composition for vulcanization includes acrylonitrile butadiene rubber (a1-1), polyvinyl chloride (a1-2), and the following formula (1):
  • the rubber composition for vulcanization is also one aspect of the present invention.
  • the rubber composition for vulcanization of the present invention comprises a non-fluorine rubber layer and a fluororubber layer, even if the non-fluorine rubber layer formed from the composition is a blend of acrylonitrile butadiene rubber and polyvinyl chloride. It can be firmly bonded.
  • NBR (a1-1) Acrylonitrile Butadiene Rubber
  • a1-1) Acrylonitrile butadiene rubber
  • NBR (a1-1) may be used without limitation for those used in the following applications. it can.
  • NBR acrylonitrile butadiene rubber
  • HNBR a hydride thereof
  • NBR (a1-1) the cold resistance, heat resistance, oil resistance, weather resistance, and extrusion moldability can be improved.
  • NBR (a1-1) preferably has a bound acrylonitrile content of 18 to 50% by mass. More preferably, it is 25 to 43% by mass. If the bound acrylonitrile content is too small, the gasoline resistance may be insufficient, and if it is too large, the adhesive strength may be reduced.
  • Polyvinyl chloride (a1-2) (hereinafter also referred to as “PVC (a1-2)”) is not particularly limited, and examples thereof include those used in the following applications, etc. Can be used.
  • NBR (a1-1) / PVC (a1-2) is preferably 90 to 50/10 to 50 by mass ratio. More preferably, it is 80-60 / 20-40. If the amount of PVC (a1-2) is too small, the ozone resistance may be insufficient, and if the amount of PVC (a1-2) is too large, the adhesive strength may decrease.
  • the rubber composition for vulcanization has the following formula (1):
  • the non-fluororubber layer (A) is a blend rubber of NBR (a1-1) and PVC (a1-2), Even if the 1,8-diazabicyclo- (5,4,0) -undecene-7 salt having a specific structure as used in JP-A-11-315966 is not used, the laminate of the present invention A fluororubber layer made of fluororubber, an acrylonitrile butadiene rubber, and a non-fluororubber layer made of polyvinyl chloride can be firmly vulcanized and bonded. Even when the rubber composition for vulcanization does not contain the compound (a2) and the fluororubber composition for forming the fluororubber layer (B)
  • the monovalent organic group having 1 to 30 carbon atoms is not particularly limited, and examples thereof include an aliphatic hydrocarbon group, an aryl group such as a phenyl group, and a benzyl group.
  • an alkyl group having 1 to 30 carbon atoms such as —CH 3 , —C 2 H 5 , —C 3 H 7, etc .; —CX 4 3 , —C 2 X 4 5 , —CH 2 X 4 , A halogen atom-containing alkyl group having 1 to 30 carbon atoms such as —CH 2 CX 4 3 and —CH 2 C 2 X 4 5
  • X 4 is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom
  • a phenyl group a benzyl A phenyl group or benzyl group in which 1 to 5 hydrogen atoms such as —C 6 F 5 or —CH 2 C 6 F 5 are substitute
  • it may contain a nitrogen atom.
  • R 1 , R 2 , and R 3 are preferably an alkyl group having 1 to 20 carbon atoms or a benzyl group from the viewpoint of improving adhesiveness.
  • X 1 in the general formula (1) is an anion, for example, a halogen ion (F ⁇ , Cl ⁇ , Br ⁇ or I ⁇ ), OH ⁇ , RO ⁇ , RCOO ⁇ , C 6 H 5 O ⁇ , SO 4 2 ⁇ , SO 3 2 ⁇ , SO 2 ⁇ , RSO 3 2 ⁇ , CO 3 2 ⁇ , NO 3 ⁇
  • R is a monovalent organic group. R represents an alkyl group having 1 to 3 carbon atoms. Preferred).
  • monovalent anions are preferable, halogen ions are more preferable, and Cl 2 ⁇ is still more preferable.
  • the content of the compound (a2) represented by the above formula (1) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass in total of NBR (a1-1) and PVC (a1-2). Moreover, since adhesiveness is excellent, 0.5 mass part or more is more preferable, and, as for content of a compound (a2), 1.0 mass part or more is still more preferable. Since the elongation of the non-fluorinated rubber layer after crosslinking is excellent, the content of the compound (a2) is preferably 5 parts by mass or less.
  • the rubber composition for vulcanization preferably contains magnesium oxide (MgO).
  • MgO magnesium oxide
  • the content of MgO is preferably 1 to 20 parts by mass with respect to a total of 100 parts by mass of NBR (a1-1) and PVC (a1-2).
  • the rubber composition for vulcanization may contain silica.
  • the silica include acidic silica (for example, trade name “Nipsil VN3” manufactured by Nippon Silica Kogyo Co., Ltd., pH is about 6) and basic silica (for example, trade name “Carplex” manufactured by Shionogi & Co., Ltd.). 1120 ", pH about 11) can be used.
  • acidic silica for example, trade name “Nipsil VN3” manufactured by Nippon Silica Kogyo Co., Ltd., pH is about 6
  • basic silica for example, trade name “Carplex” manufactured by Shionogi & Co., Ltd.
  • 1120 ", pH about 11) can be used.
  • the silica basic silica is preferable.
  • the silica is included, the content is preferably 5 to 50 parts by mass with respect to 100 parts by mass in total of NBR (a1-1) and PVC (a1-2).
  • the vulcanized rubber composition preferably contains an epoxy resin.
  • the epoxy resin also includes a thermoplastic resin having two or more epoxy groups in one molecule.
  • the epoxy resin a type obtained by a reaction of bisphenol A and epichlorohydrin, for example, “Epicoat 828” manufactured by Mitsubishi Chemical Corporation is preferably used.
  • the content of the epoxy resin is preferably an effective amount (for example, 1 part by mass) to 15 parts by mass with respect to 100 parts by mass in total of NBR (a1-1) and PVC (a1-2).
  • the rubber composition for vulcanization can improve adhesiveness, it preferably contains at least one selected from the group consisting of MgO and epoxy resin, and can improve adhesiveness. A combination of MgO and an epoxy resin is more preferable.
  • the rubber composition for vulcanization may also contain a metal oxide other than MgO.
  • metal oxides other than MgO include zinc oxide (ZnO), titanium oxide (TiO 2 ), and aluminum oxide (Al 2 O 3 ).
  • the content of the metal oxide other than MgO is preferably 1 to 15 parts by mass with respect to a total of 100 parts by mass of NBR (a1-1) and PVC (a1-2).
  • the rubber composition for vulcanization may not contain a vulcanizing agent according to NBR (a1-1) as long as it can be vulcanized, or it may be adapted to the vulcanization system of NBR (a1-1).
  • a vulcanizing agent may be contained.
  • a conventionally well-known thing can be used as said vulcanizing agent.
  • the vulcanization system of NBR (a1-1) includes sulfur vulcanization system, polyamine vulcanization system, polyol vulcanization system, peroxide vulcanization system, imidazole vulcanization system, triazine vulcanization system, oxazole vulcanization system, and thiazole. Any vulcanization system can be adopted, but if NBR (a1-1) contains a vulcanizable group (cure site), it can be selected as appropriate depending on the type of cure site or the characteristics and application to be applied to the laminate. Good.
  • the vulcanizing agent sulfur vulcanizing vulcanizing agent, polyamine vulcanizing vulcanizing agent, polyol vulcanizing vulcanizing agent, peroxide vulcanizing vulcanizing agent, imidazole vulcanizing vulcanizing agent can be used. Any of a vulcanizing agent, a triazine vulcanizing vulcanizing agent, an oxazole vulcanizing vulcanizing agent, and a thiazole vulcanizing vulcanizing agent may be employed, and they may be used alone or in combination.
  • the vulcanization system of NBR (a1-1) a sulfur vulcanization system or a peroxide vulcanization system is usually employed. Therefore, the vulcanizing agent is a sulfur vulcanizing system vulcanizing agent or a peroxide vulcanizing system vulcanizing system. It is preferably at least one selected from the group consisting of agents.
  • sulfur vulcanizing agents include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, sulfur chloride, sulfur dichloride, disulfide compounds, polysulfide compounds, and the like.
  • the compounding amount of the sulfur vulcanizing agent is preferably 1.0 to 10.0 parts by mass with respect to 100 parts by mass in total of NBR (a1-1) and PVC (a1-2). If the amount is too small, the adhesion tends to be insufficient, and if the amount is too large, it tends to be too hard.
  • the peroxide vulcanizing agent an organic peroxide that easily generates a peroxy radical in the presence of heat or a redox system is preferable.
  • organic peroxides examples include 1,1-bis (t-butylperoxy) -3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, and di-t-butyl.
  • dialkyl compounds preferred are dialkyl compounds.
  • the type and content are selected from the amount of active —O—O—, decomposition temperature and the like.
  • the content is usually 0.1 to 15.0 parts by mass, preferably 0.3 to 5.0 parts by mass with respect to a total of 100 parts by mass of NBR (a1-1) and PVC (a1-2).
  • the vulcanizing agent is preferably at least one selected from the group consisting of a sulfur vulcanizing vulcanizing agent and a peroxide vulcanizing vulcanizing agent, more preferably a peroxide vulcanizing vulcanizing agent,
  • the content thereof is preferably 0.5 to 5.0 parts by mass, particularly preferably 1.0 to 3.3 parts per 100 parts by mass in total of NBR (a1-1) and PVC (a1-2). 0 parts by mass.
  • the rubber composition for vulcanization may be used in combination with a vulcanization aid or a co-curing agent.
  • a vulcanization aid or a co-curing agent.
  • triallyl isocyanurate is preferable from the viewpoint of vulcanizability and physical properties of the vulcanizate.
  • the above vulcanizing rubber composition is prepared according to the purpose of the laminate of the present invention by adding usual additives, for example, fillers, processing aids, plasticizers, softeners, etc., to general vulcanizing rubber compositions.
  • additives for example, fillers, processing aids, plasticizers, softeners, etc.
  • various additives such as an ultraviolet absorber, an oil resistance improver, a foaming agent, a scorch inhibitor, and a lubricant can be contained.
  • these additives are contained in amounts that do not impair the adhesive strength with the fluororubber layer (B), which is the object of the present invention.
  • Fillers include metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydroxide; carbonates such as magnesium carbonate, aluminum carbonate, calcium carbonate, barium carbonate; magnesium silicate, calcium silicate, sodium silicate Silicates such as aluminum silicate; sulfates such as aluminum sulfate, calcium sulfate and barium sulfate; metal sulfides such as synthetic hydrotalcite, molybdenum disulfide, iron sulfide and copper sulfide; diatomaceous earth, asbestos, lithopone (Zinc sulfide / barium sulfide), graphite, carbon black, carbon fluoride, calcium fluoride, coke, quartz fine powder, zinc white, talc, mica powder, wollastonite, carbon fiber, aramid fiber, various whiskers, glass fiber , Organic reinforcing agents, organic fillers, etc. It is.
  • metal hydroxides such as magnesium hydroxide, aluminum hydroxide, calcium hydrox
  • higher fatty acids such as stearic acid, oleic acid, palmitic acid and lauric acid; higher fatty acid salts such as sodium stearate and zinc stearate; higher fatty acid amides such as stearic acid amide and oleic acid amide; oleic acid Higher fatty acid esters such as ethyl, higher aliphatic amines such as stearylamine and oleylamine; petroleum waxes such as carnauba wax and ceresin wax; polyglycols such as ethylene glycol, glycerin and diethylene glycol; aliphatic hydrocarbons such as petroleum jelly and paraffin; Silicone oil, silicone polymer, low molecular weight polyethylene, phthalates, phosphates, rosin, (halogenated) dialkylamine, (halogenated) dialkylsulfone, surfactant And the like.
  • higher fatty acids such as stearic acid, oleic acid, palmitic acid and la
  • plasticizers include phthalic acid derivatives and sebacic acid derivatives, softeners such as lubricating oil, process oil, coal tar, castor oil, calcium stearate, and anti-aging agents such as phenylenediamines and phosphates, Examples include quinolines, cresols, phenols, and dithiocarbamate metal salts.
  • a rubber composition for vulcanization includes a mixture of NBR (a1-1) and PVC (a1-2), a compound (a2), and, if necessary, a metal oxide such as magnesium oxide, silica, vulcanization It is prepared by kneading agents and other additives.
  • the kneading can be performed using, for example, an open roll, a Banbury mixer, a pressure kneader, or the like at a temperature of 100 ° C. or lower.
  • the fluoro rubber layer (B) is a layer formed from a fluoro rubber composition containing the fluoro rubber (b1).
  • Examples of the fluorororubber (b1) include peroxide vulcanizable fluororubber, polyol vulcanizable fluororubber, polyamine vulcanizable fluororubber, and the like. From the viewpoint of scorch resistance, a fluororubber capable of peroxide vulcanization or a fluororubber capable of polyol vulcanization is preferred.
  • the peroxide vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a peroxide vulcanizable site.
  • the peroxide vulcanizable site is not particularly limited, and examples thereof include an iodine atom and a bromine atom.
  • the polyol vulcanizable fluoro rubber is not particularly limited as long as it is a fluoro rubber having a polyol vulcanizable part.
  • the polyol vulcanizable part is not particularly limited, and examples thereof include a part having a vinylidene fluoride (VdF) unit.
  • VdF vinylidene fluoride
  • Examples of the method for introducing the vulcanization site include a method of copolymerizing a monomer that gives a vulcanization site during the polymerization of the fluororubber. From the viewpoint of heat resistance, the fluororubber (b1) is more preferably a fluororubber capable of polyol vulcanization.
  • the fluororubber (b1) is preferably a non-perfluorofluorororubber from the viewpoint of cost, and is at least selected from the group consisting of vinylidene fluoride fluororubber and tetrafluoroethylene / propylene fluororubber.
  • One type of fluororubber is more preferable.
  • the fluorine rubber (b1) include vinylidene fluoride (VdF) / hexafluoropropylene (HFP) fluorine rubber, VdF / HFP / tetrafluoroethylene (TFE) fluorine rubber, TFE / propylene fluorine rubber, and TFE.
  • VdF fluororubber examples thereof include VdF / CTFE fluororubber.
  • the fluororubber (b1) is more preferably a fluororubber containing a VdF unit (VdF fluoropolymer) from the viewpoints of heat resistance, compression set, workability, and cost.
  • VdF-HFP fluororubber and VdF- More preferred is at least one fluororubber selected from the group consisting of HFP-TFE fluororubbers.
  • said fluororubber (b1) what was demonstrated above is not restricted to 1 type, You may use 2 or more types.
  • the fluorororubber (b1) used in the present invention is preferably a fluororubber having a fluorine content of 64% by mass or more, and more preferably a fluororubber having a fluorine content of 66% by mass or more.
  • the upper limit of the fluorine content is not particularly limited, but is preferably 74% by mass or less. When the fluorine content is less than 64% by mass, chemical resistance, fuel oil resistance and fuel permeability tend to be inferior.
  • the rubber component may be composed only of the fluororubber (b1).
  • the fluororubber composition may further contain a compound (a2) represented by the formula (1). Adhesiveness can be improved more by both the rubber composition for vulcanization
  • the content of the compound (a2) represented by the formula (1) is preferably 0.1 to 10 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the fluororubber (b1). 5 parts by mass is more preferable, and the lower limit is still more preferably 0.5 parts by mass. If the content is less than 0.1 parts by mass, the adhesiveness may be inferior, and if it exceeds 10 parts by mass, the elongation of the non-fluorinated rubber layer (A) after crosslinking tends to be inferior.
  • At least one polyfunctional compound may be added to the fluororubber composition.
  • the polyfunctional compound is a compound having two or more functional groups having the same or different structures in one molecule.
  • the functional groups possessed by the polyfunctional compound are generally known to have reactivity such as carbonyl group, carboxyl group, haloformyl group, amide group, olefin group, amino group, isocyanate group, hydroxy group, and epoxy group. Any functional group can be used. These functional group-containing compounds are expected not only to have high affinity with fluororubber, but also to react with the functional group of the fluororesin to further improve the adhesion.
  • the fluororubber composition preferably further contains a vulcanizing agent.
  • the vulcanizing agent can be appropriately selected depending on the vulcanization system of the fluororubber (b1). Specifically, a peroxide vulcanizing agent, a polyol vulcanizing agent and the like can be selected according to the purpose.
  • organic peroxide is preferably one that easily generates a peroxy radical in the presence of heat or a redox system.
  • 1,1-bis (t-butylperoxy) -3,5,5-trimethyl Cyclohexane, 2,5-dimethylhexane-2,5-dihydroxy peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butylperoxy) -P-diisopropylbenzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, benzoylper Oxide, t-butylperoxybenzene, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t -Butyl peroxyisopropyl carbonate and the like can be exempl
  • dialkyl compounds are preferred.
  • the amount used is appropriately selected from the amount of active —O—O—, the decomposition temperature, and the like.
  • the amount used is usually 0.1 to 15 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the fluororubber (b1).
  • a vulcanization aid or a co-vulcanizing agent may be used in combination.
  • the vulcanization aid or co-vulcanization agent is not particularly limited, and examples thereof include the above-described vulcanization aid and co-vulcanization agent.
  • triallyl isocyanurate (TAIC) is preferable from the viewpoint of vulcanizability and physical properties of the vulcanizate.
  • the content of the vulcanization aid or co-vulcanizing agent is preferably 0.2 to 10 parts by mass, more preferably 0.5 to 6 parts by mass, with respect to 100 parts by mass of the fluororubber (b1). More preferred is 5 parts by mass. If the vulcanizing agent is less than 0.2 parts by mass, the vulcanization density tends to be low and the compression set tends to be large, and if it exceeds 10 parts by mass, the vulcanization density becomes too high and cracks during compression. It tends to be easier.
  • the polyol vulcanizing agent is not particularly limited, and for example, a polyhydroxy compound, particularly a polyhydroxy aromatic compound is preferably used from the viewpoint of excellent heat resistance.
  • the polyhydroxy aromatic compound is not particularly limited.
  • 2,2-bis (4-hydroxyphenyl) propane hereinafter referred to as bisphenol A
  • 2,2-bis (4-hydroxyphenyl) perfluoropropane (Hereinafter referred to as bisphenol AF)
  • resorcin 1,3-dihydroxybenzene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenyl, 4,4'- Dihydroxystilbene, 2,6-dihydroxyanthracene, hydroquinone, catechol, 2,2-bis (4-hydroxyphenyl) butane (hereinafter referred to as bisphenol B), 4,4-bis (4-hydroxyphenyl) valeric acid, 2, 2-bis (4-hydroxypheny
  • a polyhydroxy compound is preferable because the compression set of the fluorinated rubber after vulcanization is small and the moldability is excellent, and a polyhydroxy aromatic compound is preferable because of excellent heat resistance. More preferred is bisphenol AF.
  • the content of the polyol vulcanizing agent is preferably 0.2 to 10 parts by mass, and 0.5 to 6 parts by mass with respect to 100 parts by mass of the fluororubber (b1). More preferred is 1 to 3 parts by mass. If the content is less than 0.2 parts by mass, the vulcanization density tends to be low and the compression set tends to be large. If the content exceeds 10 parts by mass, the vulcanization density becomes too high and cracks occur during compression. It tends to be easier.
  • a vulcanization accelerator may be used in combination with a polyol vulcanizing agent.
  • the vulcanization reaction can be promoted by promoting the formation of an intramolecular double bond in the dehydrofluorination reaction of the fluororubber main chain.
  • fluororubber composition if necessary, usual additives blended in the fluororubber composition, for example, filler, processing aid, plasticizer, colorant, stabilizer, adhesion aid, acid acceptor Various additives such as mold release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc.
  • additives such as mold release agents, conductivity imparting agents, thermal conductivity imparting agents, surface non-adhesives, flexibility imparting agents, heat resistance improvers, flame retardants, etc.
  • One or more different conventional vulcanizing agents and vulcanization accelerators may be blended.
  • the fluororubber composition generally uses fluororubber (b1) and, if necessary, other additives such as a vulcanizing agent, a vulcanizing aid, a co-vulcanizing agent, a vulcanization accelerator, and a filler. It can be obtained by kneading using a rubber kneading apparatus. As the rubber kneading apparatus, a roll, a kneader, a Banbury mixer, an internal mixer, a twin screw extruder, or the like can be used.
  • the laminate of the present invention has a simple structure and can be provided with low temperature, chemical resistance and flexibility despite its low cost.
  • One of the preferred embodiments is a two-layer structure. Further, from the viewpoint of cost reduction and flexibility, the non-fluoro rubber layer (A) and the fluoro rubber are provided on one side of the fluoro rubber layer (B) (the surface on which the non-fluoro rubber layer (A) is not laminated).
  • It may be a laminate of three or more layers in which polymer layers (C) different from the layer (B) are laminated, or one side of the non-fluororubber layer (A) (the fluororubber layer (B) is laminated)
  • a non-fluorinated rubber layer (A) and a polymer layer (C) different from the fluororubber layer (B) may be laminated on three or more layers.
  • stacked on both sides of the fluororubber layer (B) may be sufficient, and a fluororubber layer ( It may be a laminate of three or more layers in which B) is laminated.
  • the laminated body of this invention can be manufactured by laminating
  • the non-fluoro rubber layer (A) and the fluoro rubber layer (B) are laminated by forming the non-fluoro rubber layer (A) and the fluoro rubber layer (B) separately and then laminating them by means such as pressure bonding. Either a method in which the layer (A) and the fluororubber layer (B) are simultaneously molded and laminated, or a method in which the fluororubber layer (B) is applied to the non-fluororubber layer (A) may be used.
  • the fluororubber molding method and the rubber composition for vulcanization are individually molded. Can be adopted.
  • Molding of the non-fluorinated rubber layer (A) is carried out by heating and compression molding method, transfer molding method, extrusion molding method, injection molding method, calender molding method, coating method, etc. for the rubber composition for vulcanization, etc. It can be set as the molded object of various shapes.
  • the fluorororubber layer (B) can be molded by a method such as heat compression molding, extrusion molding or injection molding.
  • a method such as heat compression molding, extrusion molding or injection molding.
  • commonly used fluororubber molding machines such as injection molding machines, blow molding machines, extrusion molding machines, various coating devices, etc., can be used to produce laminates of various shapes such as sheets and tubes. Is possible. Of these, the extrusion method is preferred because of its excellent productivity.
  • a vulcanized rubber composition for forming the non-fluoro rubber layer (A) and the fluoro rubber layer (B) are formed.
  • the method include laminating simultaneously with molding using the fluororubber (b1) by a multilayer compression molding method, a multilayer transfer molding method, a multilayer extrusion molding method, a multilayer injection molding method, a doubling method, and the like.
  • the non-fluororubber layer (A) and the fluororubber layer (B) can be laminated at the same time as the molding, and therefore a step of closely adhering the non-fluorine rubber layer (A) and the fluororubber layer (B) is particularly necessary. In addition, it is suitable for obtaining strong adhesion in the subsequent vulcanization step.
  • the laminate of the present invention is preferably obtained by heat treatment.
  • the non-fluoro rubber layer (A) and the fluoro rubber layer (B) can be vulcanized.
  • a bonded laminate can be obtained.
  • the heat treatment can be performed after the non-fluororubber layer (A) and the fluororubber layer (B) are stacked.
  • a non-fluororubber layer (A) and a fluororubber layer (B) can be vulcanized.
  • the non-fluorinated rubber layer (A) and the fluorinated rubber layer (B) are vulcanized.
  • the conditions for the heat treatment are not particularly limited and can be performed under normal conditions, but at 150 to 180 ° C. for 3 to 100 minutes, steam, press, oven, air bath, infrared, microwave, coating
  • the treatment is preferably performed using resin vulcanization or the like. More preferably, it is carried out at 160 ° C. for 20 to 45 minutes.
  • the non-fluororubber layer (A) and the fluororubber layer (B) are vulcanized and bonded, and a strong interlayer adhesion is generated.
  • the laminate of the present invention is prepared by, for example, extruding a fluororubber composition and a vulcanizing rubber composition (non-fluororubber composition) with an extruder to produce a non-fluororubber sheet and a fluororubber sheet, respectively.
  • the fluororubber sheet and the fluororubber sheet can be overlapped and inserted into a heated mold to be vulcanized and bonded.
  • the laminate of the present invention comprises a fluororubber composition and a vulcanizing rubber composition that are coextruded in two layers or two or more layers by an extruder, or an inner layer by two or two or more extruders.
  • the laminated body composed of the inner layer and the outer layer can be extruded and integrated by extruding the outer layer on the upper layer, and then vulcanized and bonded by heating.
  • the laminate of the present invention is excellent in ozone resistance, as well as low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, etc. It can withstand use. Therefore, it can be used for various purposes.
  • basic electrical components such as engine bodies, main motion systems, valve systems, lubrication / cooling systems, fuel systems, intake / exhaust systems, drive system transmission systems, chassis steering systems, brake systems, and electrical components for automobile engines , Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact type and contact type packings (self-seal packing, pistons, etc.) Rings, split ring type packings, mechanical seals, oil seals, etc.), bellows, diaphragms, hoses, tubes, electric wires, etc.
  • basic electrical components such as engine bodies, main motion systems, valve systems, lubrication / cooling systems, fuel systems, intake / exhaust systems, drive system transmission systems, chassis steering systems, brake systems, and electrical components for automobile engines , Gaskets that require heat resistance, oil resistance, fuel oil resistance, LLC resistance, and steam resistance, and non-contact type and contact type packings (self-seal packing, pistons, etc.) Rings, split ring type packings,
  • gaskets such as general gaskets, seals such as O-rings, packing, timing belt cover gaskets, hoses such as control hoses, anti-vibration rubber for engine mounts, hydrogen Sealing material for high pressure valves in storage systems.
  • Fuel system fuel pump oil seal, diaphragm, valve, etc.
  • Filler (neck) hose fuel supply hose, fuel return hose, fuel hose such as vapor (evaporation) hose, fuel tank in-tank hose, filler seal, tank
  • carburetors such as packing, in-tank fuel pump mount, fuel pipe tube body and connector O-ring, fuel injector injector cushion ring, injector seal ring, injector O-ring, pressure regulator diaphragm, check valve, etc.
  • CAC composite air control
  • Transmission-related bearing seals oil seals, O-rings, packings, torque converter hoses, etc. AT transmission oil hoses, ATF hoses, O-rings, packings, etc.
  • Brake oil seal O-ring, packing, brake oil hose, etc. Master back atmospheric valve, vacuum valve, diaphragm, etc. Master cylinder piston cup (rubber cup), caliper seal, boots, etc.
  • Tubes for harness exterior parts such as electric wire (harness) insulators and sheaths of basic electrical components.
  • O-rings In addition to automobiles, for example, oil, chemical, heat, steam, or weather resistant packings, O-rings, hoses, other sealing materials, diaphragms, valves, chemicals, etc. Similar packings in plants, O-rings, seals, diaphragms, valves, hoses, rolls, tubes, chemical coatings, linings, similar packings in food plant equipment and food equipment (including household products), O- Rings, hoses, seals, belts, diaphragms, valves, rolls, tubes, similar packings in nuclear power plant equipment, O-rings, hoses, seals, diaphragms, valves, tubes, similar packings in general industrial parts, O-ring, hose, sealing material, diaphragm Is suitable valves, rolls, tubes, linings, mandrels, electric wires, flexible joints, belts, rubber plates, weather strips, the application to a roll blade PPC copying machine.
  • the laminate of the present invention is particularly suitable as a fuel hose in terms of ozone resistance, heat resistance, and low fuel permeability.
  • the laminated body of this invention is suitable as fuel piping.
  • the fuel pipe can be manufactured by an ordinary method and is not particularly limited. Further, the fuel pipe includes a corrugated tube.
  • NIPOL 1203W Mixture of 70 parts by weight of acrylonitrile butadiene rubber-30 parts by weight of polyvinyl chloride, ZnO manufactured by Nippon Zeon Co., Ltd., zinc oxide, N330 manufactured by Sakai Chemical Industry Co., Ltd., carbon black, N550 manufactured by Tokai Carbon Co., Ltd. Carbon black, manufactured by Tokai Carbon Co., Ltd., stearic acid: manufactured by Kao Co., Ltd. 4010NA: N-isopropyl-N′-phenylbenzene-1,4-diamine, Beijing Huarui United Rubber Chemical Corp. ANTAGE RD manufactured by: Kawaguchi Chemical Industry Co., Ltd.
  • Daiel TM G558 polyol-crosslinked fluororubber, VdF / TFE / HFP copolymer, manufactured by Daikin Industries, Ltd.
  • NICC5000 manufactured by Inoue Lime Industry Co., Ltd.
  • MA-150 magnesium oxide, manufactured by Kyowa Chemical Industry Co., Ltd., N774: Carbon black, manufactured by Tokai Carbon Co., Ltd.
  • Example 1 (Preparation of uncrosslinked non-fluorinated rubber sheet)
  • the materials shown in Table 1 were kneaded using an 8-inch open roll whose temperature was adjusted to 25 ° C. to obtain an uncrosslinked non-fluorinated rubber sheet (rubber composition for vulcanization) having a thickness of about 2 mm.
  • each numerical value of Table 1 represents a mass part.
  • the maximum torque value (M H ) and the minimum torque value (M L ) are measured at 160 ° C. using an MDR (model number: MDR-2000, manufactured by Alpha Technology) for the rubber composition for vulcanization.
  • the optimum vulcanization time (T 90 ) was determined. The measurement results are shown in Table 1.
  • T 90 is ⁇ (M H ) ⁇ (M L ) ⁇ ⁇ 0.9 + M L
  • T 50 is ⁇ (M H ) ⁇ (M L ) ⁇ ⁇ 0.5 + M L
  • T 10 is ⁇ (M H ) - a (M L) ⁇ ⁇ 0.1 + M L become time
  • M H and M L is the value measured according to JIS K 6300-2.
  • a non-crosslinked non-fluorinated rubber sheet having a thickness of about 2 mm and an uncrosslinked fluororubber sheet were overlapped and inserted into a heated mold, and crosslinked at 160 ° C. for 50 minutes to obtain a sheet-like laminate.
  • the obtained laminate was cut into strips having a width of 25 mm and a length of 100 mm to obtain test pieces, and a T peel test was performed at 23 ° C. at a peel rate of 50 mm / min to measure the adhesive strength. The test was performed 3 times, and the average value is shown in Table 1.
  • Mechanical properties (100% modulus (100% M), tensile strength at break (TS), tensile elongation at break (EL), hardness (Hs (SHORE A. Peak) and Hs (SHORE A. 1 sec)) of each layer obtained are shown. The measurement was performed by the following method, and the results are shown in Table 1.
  • Tensile strength at break (TS) It measured according to JIS K6251.
  • Examples 2 to 8 and Comparative Examples 1 to 3 A sheet-like laminate was produced in the same manner as in Example 1 except that the compounding agent of the vulcanizing rubber composition was changed as shown in Table 1 or 2. The evaluation results are shown in Table 1 or 2.
  • the laminate of the present invention is excellent in ozone resistance, as well as low fuel permeability, heat resistance, oil resistance, fuel oil resistance, LLC resistance, steam resistance, etc. It can withstand use. Therefore, it can be used for various applications such as automotive applications and food rubber seal material applications.

Abstract

L'objectif de la présente invention consiste à produire un corps stratifié dans lequel une couche de fluorocaoutchouc et une couche de non-fluorocaoutchouc comprenant du caoutchouc de butadiène acrylonitrile et du polychlorure de vinyle peuvent être fermement liées par vulcanisation. La présente invention est un corps stratifié caractérisé en ce qu'une couche de non-fluorocaoutchouc (A) est constituée d'une composition caoutchouteuse pour vulcanisation, la composition caoutchouteuse pour vulcanisation contenant du caoutchouc de butadiène acrylonitrile (a1-1), du polychlorure de vinyle (a1-2), et un composé (a2) représenté par la formule (1) (Dans la formule, R1, R2 et R3 sont identiques ou différents, et peuvent être un atome d'hydrogène ou un groupe organique monovalent C1-C30, et X1 est un anion.), et la couche de fluorocaoutchouc (B) est constituée d'une composition de fluorocaoutchouc contenant un fluorocaoutchouc (b1).
PCT/JP2014/051851 2013-02-08 2014-01-28 Corps stratifié WO2014123037A1 (fr)

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CN107365439B (zh) * 2017-07-30 2020-02-18 华南理工大学 一种新型的氯丁橡胶硫化方法
CN111117009A (zh) * 2018-10-30 2020-05-08 中国科学院金属研究所 一种钒电池用密封材料及其制备方法

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