CN102453284A - Rubber composition for bladder and bladder - Google Patents
Rubber composition for bladder and bladder Download PDFInfo
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- CN102453284A CN102453284A CN2011102451030A CN201110245103A CN102453284A CN 102453284 A CN102453284 A CN 102453284A CN 2011102451030 A CN2011102451030 A CN 2011102451030A CN 201110245103 A CN201110245103 A CN 201110245103A CN 102453284 A CN102453284 A CN 102453284A
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- rubber
- air bag
- masterbatch
- zinc oxide
- mass parts
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
- B29C43/32—Component parts, details or accessories; Auxiliary operations
- B29C43/36—Moulds for making articles of definite length, i.e. discrete articles
- B29C43/3642—Bags, bleeder sheets or cauls for isostatic pressing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D30/00—Producing pneumatic or solid tyres or parts thereof
- B29D30/06—Pneumatic tyres or parts thereof (e.g. produced by casting, moulding, compression moulding, injection moulding, centrifugal casting)
- B29D30/0601—Vulcanising tyres; Vulcanising presses for tyres
- B29D30/0645—Devices for inserting vulcanising cores, i.e. bladders, into the tyres; Closing the press in combination herewith
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
- C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
- C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
The present invention provides a rubber composition for a bladder, which sufficiently prolongs service life of the bladder; and the bladder which is manufactured therefrom. The rubber composition for the bladder according to the utility model comprises the following components: a rubber component; and a master batch which can be obtained through mixing at least one member selected from zinc oxide, ethylene-propylene-diene copolymer and butyl rubber (A).
Description
Technical field
The present invention relates to a kind of air bag and use rubber combination; And by the air bag of its production.
Background technology
In tire production, assembly is formed and is molded and is green tire, and green tire stands sulfuration subsequently, has the vulcanized rubber structure of caoutchouc elasticity so that produce.In sulfuration, usually, mould is attached to jacketed type pressing plate (jacket-type platen), and thus from the indirect heating tire, and a bag shape air bag inserts inside tires and water vapour etc. is injected air bag simultaneously, and heats tire thus internally.
When tire was inner heated, air bag stands because the oxygen in the water vapour or harmful acidic substance of during tyre vulcanization, producing for example hydrogen sulfide and caused oxidative degradation of nitric acid and polymer unwinds.In addition, when tire was pulled down, air bag was exposed in the air when keeping the condition of high temperature air bag at every turn.This exposure also causes the oxidative degradation that air bag is outside.
Simultaneously, common air bag comprises zinc oxide, and this zinc oxide is with acting on the sorbent material of this harmful acidic substance and prolonging the air bag life-span.For prolongs life, importantly improve the dispersiveness of zinc oxide; Yet common kneading method for example uses those methods of Banbury mixing tank that enough dispersivenesses are not provided, and therefore, can not fully obtain the function as sorbent material.In addition, the zinc oxide aggegation, thus as breaking nuclear (rupture nuclei), cause crackle thus.
Patent documentation 1 discloses air bag and has used rubber combination, wherein, mixes a large amount of sulphur, so that prevent the aggegation of zinc oxide and prolong the air bag life-span.Yet the air bag life-span still is supposed to further prolong.Patent documentation 2 discloses the tread rubber compsn that comprises zinc oxide fine powder (finely-divided zinc oxide).Yet the zinc oxide fine powder disperses insufficient, and the air bag life-span also still is supposed to further prolong.In addition, this patent documentation and not mentionedly rubber combination is applied to air bag uses rubber combination.
Patent documentation 1:JP 2005-75891A
Patent documentation 2:JP 2008-101127A
Summary of the invention
The object of the present invention is to provide a kind of air bag to use rubber combination, said compsn can address the above problem, and enough obtains the long air bag life-span; And the air bag of producing thus.
The inventor has carried out various researchs for the purpose that prolongs the air bag life-span; Therefore; The inventor finds that the use of masterbatch (masterbatch) causes the improvement that cohesive force descends and zinc oxide is dispersed of zinc oxide; Fully prolong the air bag life-span thus, said masterbatch can be through at least one acquisition of mixed oxidization zinc and ethylene-propylene-diene copolymer and butyl rubber (A).
In other words, the present invention relates to air bag and use rubber combination, said compsn comprises: rubber components; And masterbatch, the masterbatch that said masterbatch obtains through at least one and zinc oxide in mixed ethylene-propylene diene copolymerized thing and the butyl rubber (A).
With respect to the zinc oxide of 100 mass parts in the said masterbatch, the total amount of ethylene-propylene-diene copolymer and butyl rubber (A) is preferably 10～180 mass parts.
Preferred masterbatch further comprises the vinyl-vinyl acetate copolymer that is mixed in wherein.
With respect to the rubber components of 100 mass parts, the amount that is derived from the zinc oxide of masterbatch is preferably 0.5～10 mass parts.
Based on the rubber components of 100 quality %, the preferred rubber compsn comprises the butyl rubber (B) of 90～100 quality % and the X 050 of 0～10 quality %.
Preferred masterbatch further comprises the cross-linked resin that is mixed in wherein.
The invention still further relates to a kind of air bag of producing by above-mentioned rubber combination.
Use rubber combination because the invention provides the air bag that comprises specific masterbatch, so the air bag life-span can fully be prolonged.Therefore, exchange the number of air bag (exchanging bladders) in the time of can reducing tire production, and can improve the productivity of tire production.
Embodiment
Air bag of the present invention comprises with rubber combination: rubber components; And can be through the masterbatch (MB) of at least one acquisition in mixed oxidization zinc and ethylene-propylene-diene copolymer and the butyl rubber (A).
[masterbatch]
At first, hereinafter masterbatch is described.
Masterbatch can be through at least one acquisition in mixed oxidization zinc and ethylene-propylene-diene copolymer and the butyl rubber (A)..
The example of zinc oxide comprise be generally used for rubber industry those zinc oxide (for example; The zinc oxide that Mitsu Mining & Smelting Co., Ltd produces) and the zinc oxide fine powder (finely-divided zinc oxide) with the following average primary particle diameter of 200nm (for example; HakusuiTech Co., the ZINCOX SUPER F-1 that Ltd. produces).It particularly preferably is the zinc oxide fine powder, because can fully prolong the air bag life-span.
The average primary particle diameter of zinc oxide fine powder is preferably below the 200nm, and more preferably below the 130nm.And the average primary particle diameter of zinc oxide is preferably more than the 20nm, and more preferably more than the 30nm.Zinc oxide with particle diameter in the above-mentioned scope can fully prolong the air bag life-span.
In the present invention, average primary particle diameter is the median size of changing by through the specific surface area of measuring based on the BET method of nitrogen absorption (average primary particle diameter).
Ethylene-propylene-diene copolymer (EPDM) is based on the material of the multipolymer of ethylene-propylene rubber, ethene and propylene, and through the 3rd component relatively in a small amount is incorporated in the multipolymer, said EPDM has two keys in polymer molecule.Not as butyl rubber, EPDM has few two keys similar with butyl rubber to EPDM simultaneously aspect ventilation property and anti-steam deterioration, and on for the weather resistance of aging, ozone and chemical remarkably.
The example of the 3rd component comprises: ethylidene norbornene (ENB), 1,4-hexadiene and Dicyclopentadiene (DCPD).
Can suitably use commercially available EPDM, for example ESPRENE EPDM series (Sumitomo Chemical Co's production) and EP 96 (JSR Corp.'s production).
The example of butyl rubber (A) comprises halogenated butyl rubber (X-IIR) for example brominated butyl rubber (Br-IIR) and Chlorobutyl (Cl-IIR) and butyl rubber (IIR) (hereinafter, be different from halogenated butyl rubber, be also referred to as not halogenated butyl rubber).Each of these butyl rubbers (A) can use separately, also can two or more combinations use.Because its high heat resistance, halogenated butyl rubber not preferably in these butyl rubbers (A).
The amount of isoprene is preferably below the 3mol% in halogenated butyl rubber not, and more preferably below the 2mol%.If should measure greater than 3mol%, the thermotolerance of air bag possibly descend so, and therefore the life-span of air bag unlikely is extended.The amount of isoprene is preferably more than the 0.5mol% in halogenated butyl rubber not, and more preferably more than the 0.7mol%, and more than the further preferred 1mol%.If should measure, be not enough to so through crosslinked improvement rubbery intensity, and therefore the life-span of air bag possibly shorten less than 0.5mol%.
Usually, butyl rubber (A) only has the two keys below 0.5%, even and rubber cross, number of crosslinks is also extremely low.Butyl rubber (A) is usually through mixing iso-butylene and isoprene monomer and reaction is produced.
Preferred masterbatch further comprises the vinyl-vinyl acetate copolymer (EVA) that is mixed in wherein.The use of EVA has improved the dispersiveness of zinc oxide, and causes thus enough air bag life-spans.In addition, this masterbatch can granulation (curing) and weighing automatically, obtains enough manipulative capabilities thus.The effect that causes good especially prolongs life is used in the combination of EVA and EPDM in masterbatch.
Preferred masterbatch further comprises the cross-linked resin that is mixed in wherein.In this case, can improve the dispersiveness of zinc oxide, and the zinc oxide in the masterbatch can provide suitable kneading moment of torsion (kneading torque), improve the dispersiveness of cross-linked resin itself thus.Therefore, can obtain enough air bag life-spans.
The example of cross-linked resin comprises the alkyl resinox.The not special restriction of the type of alkyl resinox; Because its outstanding thermotolerance does not preferably have halogenated not halogenated resin.Common alkyl resinox has the methylol of 7～10 quality %.
Masterbatch can be through any method production, as long as component is mixed (kneading) in wherein.The example of working method comprises following method: wherein; At least a and EVA (if desired) in EPDM and the butyl rubber (A) carries out mastication; Mediate mixture with preparation; Then, mediate the kneading mixture and zinc oxide and the cross-linked resin (if desired) that are obtained, thus the preparation masterbatch.
Mastication can carry out through arbitrary ordinary method with mediating, and not restriction.For example, can suitably use Banbury mixer for example banbury mixers, kneader, mill etc.
In the production of masterbatch, the mastication condition generally is 80 ℃～200 ℃ and 3～10 minutes.In addition, kneading condition generally is 120 ℃～200 ℃ and 3～10 minutes.These conditions provide effect of the present invention well.
(composition of masterbatch)
In masterbatch, with respect to 100 mass parts zinc oxide, more than preferred 10 mass parts of the total amount of EPDM and butyl rubber (A), and more preferably more than 20 mass parts.If total amount is lower than 10 mass parts, be difficult to so produce and mediate moment of torsion, the dispersiveness of zinc oxide maybe be relatively poor, and for predetermined masterbatch, the amount of sticker (EPDM and/or butyl rubber (A)) maybe be too small, so that the air bag life-span possibly shorten.In masterbatch, with respect to the zinc oxide of 100 mass parts, this total amount is preferably below 180 mass parts, more preferably below 100 mass parts, and further below preferred 40 mass parts.If this total amount surpasses 180 mass parts, zinc oxide possibly disperse insufficiently so, and therefore shortens the air bag life-span unfriendly.
Under the situation of EPDM and EVA combination use, with respect to 100 mass parts zinc oxide in the said masterbatch, more than preferred 10 mass parts of its total amount, and more preferably more than 20 mass parts.And, below preferred 180 mass parts of this total amount, more preferably below 100 mass parts, and further below preferred 50 mass parts.If this total amount in above-mentioned scope, so the dispersiveness of zinc oxide can fully improve and the amount of sticker optimised.Therefore, can obtain effect of the present invention well.
If a large amount of stickers are blended in the masterbatch, the performance of masterbatch is not so good as butyl rubber so, and in final kneading, the carbon black of sneaking into usually in the rubber combination can not fully be sneaked in the sticker.Therefore, in reinforcement problem possibly take place.
Use in combination under the situation of EPDM and EVA, consider dispersiveness, can suitably regulate the amount of EVA; Based on EPDM and the EVA of 100 quality %, more than the preferred 3 quality % of the amount of EVA.And below the preferred 60 quality % of the amount of EVA, and more preferably below the 30 quality %.If its amount exceeds above-mentioned scope, EVA is not enough to demonstrate the effect of improving the zinc oxide dispersiveness so.
In this manual, in masterbatch of the present invention, polymeric constituent (for example, EPDM, butyl rubber (A), EVA and cross-linked resin) is and rubber components (for example, butyl rubber (B) and X 050) different concept.
Be contained in the zinc oxide in the rubber combination of the present invention based on 100 quality %, in order to improve the dispersiveness of zinc oxide, its usage ratio in masterbatch is preferably more than the 80 quality %, more preferably more than the 90 quality %, and further is preferably 100 quality %.
In addition, in rubber combination of the present invention, with respect to the following rubber components (separating the blended rubber components with masterbatch) of 100 mass parts, the amount of zinc oxide is preferably more than 1 mass parts, and more preferably more than 3 mass parts.And, below preferred 20 mass parts of the amount of zinc oxide, and more preferably below 10 mass parts.If the amount of zinc oxide in above-mentioned scope, can obtain effect of the present invention so well.
Being contained in the example that separates the rubber in the blended rubber components with masterbatch comprises: non-elastoprene, for example butyl rubber; And elastoprene, for example ethylene-propylene-elastoprene (EPDM), tree elastomer (NR), synthetic polyisoprene (IR), divinyl rubber (BR), SBR styrene butadiene rubbers (SBR), epoxy natural rubber (ENR), acrylonitrile-butadiene rubber (NBR), X 050 (CR) and styrene-isoprene-butadiene copolymer rubber (SIBR).Among these, for anti-deterioration (antioxidant decomposition), splitting resistance, chemical resistant properties and the vulcanization rate of full-scope safeguards air bag rubber combination, preferably combination is used butyl rubber (B) and CR.
The not special restriction of butyl rubber (B) (separating the blended butyl rubber) with masterbatch, and can be fit to use and the identical rubber of butyl rubber (A).
Based on the rubber components of 100 quality %, more than the preferred 90 quality % of the amount of butyl rubber (B), and more preferably more than the 92 quality %.If the amount of butyl rubber is lower than 90 quality %, can reduce the thermotolerance of rubber combination, anti-deterioration, splitting resistance, chemical resistant properties, and may not prolong the air bag life-span.And based on the rubber components of 100 quality %, the amount of butyl rubber (B) can be 100 quality %, but below the preferred 97 quality %, and more preferably below the 95 quality %.If the amount of butyl rubber (B) surpasses 97 quality %, possibly be difficult to so provides needed hardness and tensile strength to air bag.
Under the situation of mixed C R, based on the rubber components of 100 quality %, more than the preferred 1 quality % of the amount of CR, and more preferably more than the 3 quality %.If the amount of CR is lower than 1 quality %, possibly be difficult to so provides needed rigidity to air bag.And, based on the rubber components of 100 quality %, below the preferred 10 quality % of the amount of CR, and more preferably below the 7 quality %.If the amount of CR surpasses 10 quality %, the relative proportion of butyl rubber is lower so, and thermotolerance maybe be not enough.
If the amount of CR is below the 3 quality %, fluff owing to the crosslinked of cross-linked resin so.Therefore, used masterbatch preferably comprises butyl rubber (A) and cross-linked resin.
Generally speaking, rubber combination of the present invention further comprises with masterbatch and separates the blended cross-linked resin.Therefore, can obtain effect of the present invention well.The not special restriction of cross-linked resin, and can suitably use with masterbatch in the identical resin of cross-linked resin.
With respect to the rubber components of 100 mass parts, in the masterbatch more than preferred 2 mass parts of total amount of cross-linked resin and other cross-linked resin, and more preferably more than 5 mass parts.And, below preferred 20 mass parts of this total amount, and more preferably below 15 mass parts.If this total amount in above-mentioned scope, can obtain effect of the present invention so well.
Based on the total amount of cross-linked resin in the 100 quality % masterbatch and other cross-linked resin, the amount of cross-linked resin is preferably 10～100 quality % in the masterbatch.If should measure in above-mentioned scope, can obtain effect of the present invention well so.
Generally speaking, rubber combination of the present invention comprises carbon black.Used sooty example includes but not limited to GPF, FEF, HAF, ISAF and SAF.Sooty mixes has increased reinforcement.
Carbon black preferably has 40m
2Above and the more preferably 60m of/g
2Nitrogen adsorption specific surface area (the N that/g is above
2SA).If N
2SA is lower than 40m
2/ g, reinforcement maybe be not enough so, and the air bag life-span possibly shorten.Sooty N
2The preferred 120m of SA
2Below/the g, and more preferably 100m
2Below/the g.If N
2SA is higher than 120m
2/ g, filler possibly be difficult to disperse so, and splitting resistance (weather resistance) possibly reduce, and product maybe local hardening, possibly cause the short air bag life-span.
Here, sooty nitrogen adsorption specific surface area is measured according to the A method of JIS K6217.
Under the situation of mixed carbon black, with respect to 100 mass parts rubber components, more than preferred 40 mass parts of sooty amount, and more preferably more than 50 mass parts.If content is lower than 40 mass parts, reinforcement maybe be not enough so.And, with respect to 100 mass parts rubber components, below preferred 80 mass parts of sooty amount, and more preferably below 70 mass parts.If the sooty amount is greater than 80 mass parts, filler possibly be difficult to disperse so, and splitting resistance (weather resistance) possibly reduce, and product maybe local hardening, possibly cause the short air bag life-span.
Except above-mentioned composition; Air bag of the present invention can further comprise with rubber combination: oils, inhibitor, releasing agent, Triple Pressed Stearic Acid, mineral filler are (for example; WHITE CARBON BLACK, silicon-dioxide, treated carbonates, talcum and aluminum oxide), organic reinforcing agent (for example, HI high impact styron, coumarone-indene resin, resol, xylogen, modification melamine resin and petroleum resin), heat resistance improver (heat-resistance improver), fire retardant, be used to reagent of giving thermal conductivity etc.
Rubber combination preferred package oil-containing among the present invention.The mixing of oil has improved processibility and has increased rubbery intensity.Oil example comprise process oil, vegetablefats and oil, and composition thereof.Among these oil, what be fit to use is vegetablefats and oil and Viscotrol C, because their unlikely volatilizations, and therefore they can flow on the balloon surface, and prevents the bonding with cover tire.
Comprise under the oil condition at rubber combination of the present invention, with respect to the rubber components of 100 mass parts, more than preferred 0.5 mass parts of content of oil, and more preferably more than 1 mass parts.If the amount of oil is lower than 0.5 mass parts, so maybe be bonded to one another at sulfuration rear gasbag and cover tire.And, with respect to 100 mass parts rubber components, below preferred 10 mass parts of amount of oil, and more preferably below 7 mass parts.If the amount of oil is greater than 10 mass parts, the relative proportion of butyl rubber is lower, and the air bag life-span trends towards shortening.
With respect to inhibitor, for example, can suitably use and improve stable on heating phenolic antioxidant (for example, single phenolic antioxidant, bisphenol antioxidant and polyphenol antioxidation agent.
Rubber combination of the present invention preferably comprises releasing agent.Therefore, under the situation of mixing cross-linked resin, can prevent the adhesion of cross-linked resin to banbury mixers inside.The example that is fit to the releasing agent of use comprises the mixture of fatty acid metal salt and fatty acid amide.With respect to the rubber components of 100 mass parts, the amount of releasing agent is preferably 0.1～10 mass parts.
Air bag of the present invention can pass through mixed rubber component, masterbatch and other component (for example, carbon black) with rubber combination and prepare.For example, rubber combination can be produced through following method.
At first, the kneading operation is described.The kneading operation of this embodiment comprises: basic kneading step and final kneading step.In mediating operation, for example, use kneader device to mediate said components.Can use any conventional kneader device, and its example comprises Banbury kneader, kneader and mill.
<basic kneading step >
In basic kneading step, for example, use kneader device to mediate said components except masterbatch, cross-linked resin and releasing agent (that is, butyl rubber, carbon black, oil, X 050 and inhibitor etc.),
In order to ensure employed dispersity of carbon black and to suppress the pyrolysis of thermotolerance not as the rubber (for example X 050) of butyl rubber, so basic kneading step preferably is divided into following two sub-steps (sub-steps) (mediate on first basis and mediate on second basis).
< the first basic kneading step >
In the first basic kneading step, for example, use kneader device to mediate and comprise butyl rubber, carbon black and oily component.
In the first basic kneading step, be that 10 ℃～40 ℃ rubber stock is mediated when preferably this kneading being begun, arrive 150 ℃～180 ℃ up to its temperature.If the temperature of rubber stock is lower than 150 ℃ when mediating end, be difficult to ensure dispersity of carbon black so.And if temperature is higher than 180 ℃, so because gelification possibly take place carbon black, so that the homogeneity of the thin slice of the rubber combination of warp kneading maybe be relatively poor.
< the second basic kneading step >
In the second basic kneading step, for example, the rubber stock of in the first basic kneading step, mediating further mixes with the component that comprises X 050 and inhibitor, and uses kneader device to mediate.In the second basic kneading step, be that 10 ℃～40 ℃ gained rubber stock is mediated when preferably this kneading being begun, arrive 120 ℃～140 ℃ up to its temperature.If the temperature of rubber stock is lower than 120 ℃ when mediate accomplishing, possibly be difficult to ensure the dispersiveness of X 050 so, and the homogeneity of the air bag rubber combination of being produced possibly descend, so that possibly shorten the air bag life-span.And if temperature is higher than 140 ℃, the pyrolysis of X 050 possibly take place so, so that the air bag life-span trends towards shortening.
< final kneading step >
In final kneading step, for example, the rubber stock of in the second basic kneading step, mediating is further with masterbatch, mixes with the component that comprises cross-linked resin and releasing agent if desired, and the use kneader device is mediated.In the present invention, use masterbatch; Therefore, even use the zinc oxide fine powder that is difficult to good distribution, the zinc oxide fine powder also can not carry out repeatedly fully dispersion under the final situation of mediating.Therefore, the air bag that can effectively produce longer life is used rubber combination.
In final kneading step, be that the rubber stock of room temperature (normal temperature) is mediated when preferably this kneading being begun, arrive 90 ℃～105 ℃ up to its temperature.If the temperature of rubber stock is lower than 90 ℃ when mediating end, the uniformly dispersed of zinc oxide maybe be not enough so.And if temperature is higher than 105 ℃, crosslinking reaction possibly begin so.
In addition, in final kneading step, consider the prevention of the dispersiveness and the crosslinking reaction of zinc oxide, the rotation number of kneader device is preferably 20～45rpm.
< crosslinking reaction step >
After above-mentioned kneading step, carry out the crosslinking reaction step, use rubber combination to obtain air bag of the present invention.In the crosslinking reaction step, for example, the rubber combination (uncrosslinked rubber combination) that in final kneading step, obtains can descend crosslinked 30～240 minutes at 170 ℃～200 ℃.
Rubber combination among the present invention is suitable as tire production and uses air bag.
Air bag can be produced through following steps: use forcing machine with the shape of uncrosslinked rubber combination extrusion moulding as air bag, crosslinked then inflatable balloon-like rubber combination.
Embodiment
The present invention will be elaborated according to embodiment, but the present invention is not limited to these embodiment.
The chemical that is used for embodiment is listed in as follows.
Butyl rubber 268:BUTYL 268 (ExxonMobil Chemical manufactured, isoprene content: 1.7mol%) (not halogenated butyl rubber)
Butyl rubber 065:BUTYL 065 (ExxonMobil Chemical manufactured, isoprene content: 1.05mol%) (not halogenated butyl rubber)
X 050: Neoprene W (Showa Denko K. K's manufacturing)
(Cabot Japan Co., Ltd. makes carbon black: SHOBLACK N 330, N
2SA:75m
2/ g)
Viscotrol C: No. 1 technical grade Viscotrol C (rich state system oil Co., Ltd. makes)
Inhibitor: NOCRAC NS-5 (the emerging chemical industry of imperial palace Co., Ltd. makes, and 2,2 '-methylene-bis(4-ethyl-6-t-butyl phenol))
Releasing agent: WB 16 (Struktol makes, the mixture of fatty acid metal salt (fatty acid calcium) and fatty acid amide)
Cross-linked resin: TACKIROL 201 (Taoka Chemical Industries Co. Ltd. makes, the alkyl resinox)
Zinc oxide (1): No. two (Mitsu Mining & Smelting Co., Ltd makes zinc white, average primary particle diameter: 270nm)
Zinc oxide (2): (HakusuiTech Co., Ltd. makes zinc oxide ultra-fine powder F-1, average primary particle diameter: 100nm)
EPDM:ESPRENE EPDM 301A (Sumitomo Chemical Co's manufacturing)
EVA:EVATATE EVA (Sumitomo Chemical Co's manufacturing)
Ratio (ratio of mixture) that it should be noted that the EPDM/EVA in MB1 and 2 is 1/1 (mass ratio).
(making example)
(preparation of MB)
According to prescription shown in the table 2, use banbury mixers that EPDM, EVA and IIR are carried out mastication, and be heated to about 100 ℃.Then, will more a spot of zinc oxide and cross-linked resin optionally pour in the mixing machine, and mediate mixture, so that outflow temperature (discharging temperature) is about 130 ℃.Thus, obtain masterbatch.
(comparative example)
According to prescription shown in the table 1; Will be not halogenated butyl rubber (butyl rubber 065 and butyl rubber 268), carbon black and Viscotrol C insert in the 240L banbury mixers with packing factor of 70%, and mediate until temperature and arrive 160 ℃ (mediating the beginning temperature is 30 ℃).After mixture cooling, X 050 and inhibitor are added in the mixture and mediate, so that temperature is increased to 130 ℃ from 30 ℃.Mixture is further cooled off, mediate with zinc oxide and cross-linked resin then, so that temperature is increased to 100 ℃ (first final kneading steps) from 30 ℃.Subsequently, mediate mixture and be cooled to 30 ℃ (cooling steps) for the first time, and once more it is put in the banbury mixers.Mediate mixture and arrive 100 ℃ (second finally mediates ((re-milling) once more mills) step), and obtain uncrosslinked rubber combination thus until it.
(embodiment)
According to prescription shown in the table 2; Under the condition identical, obtain uncrosslinked rubber combination with comparative example; Different is adds the masterbatch, releasing agent and the cross-linked resin that are obtained in the above-mentioned manufacturing example replacing zinc oxide in the first final kneading step, and does not carry out cooling step and second and finally mediate (milling once more) step.
With the uncrosslinked rubber combination mold pressing that is obtained is the shape of air bag, descends crosslinked 30 minutes at 200 ℃ then.Thus, produce air bag (tire size: 195/65R15, for the air bag stretch ratio of mold pressing shape (periphery (periphery): 1.08, circumference (circumference): 1.25), air bag specification: 5mm).
The air bag that is obtained is used for the shaping (Cure Conditions of Tire: 180 ℃ and 12 minutes) of tire.Inspection is because come off (layering) that the inner rubber combination thermal destruction of air bag occurs.If the stratified layer growth that is checked through from the rubber combination of air bag inside is more than the 5mm, be considered to air bag life-span number at this time access times so.
[table 1]
In the embodiment that uses masterbatch, its air bag life-span number is greater than the air bag life-span number in the comparative example.
Claims (7)
1. an air bag is used rubber combination, and it comprises:
Rubber components; And
Masterbatch, said masterbatch obtains with zinc oxide through in mixed ethylene-propylene diene copolymerized thing and the butyl rubber (A) at least one.
2. air bag as claimed in claim 1 is used rubber combination, it is characterized in that,
With respect to 100 mass parts zinc oxide in the said masterbatch, the total amount of ethylene-propylene-diene copolymer and butyl rubber (A) is 10～180 mass parts.
3. air bag as claimed in claim 1 is used rubber combination, it is characterized in that,
Said masterbatch further comprises the vinyl-vinyl acetate copolymer that is mixed in wherein.
4. air bag as claimed in claim 1 is used rubber combination, it is characterized in that,
With respect to the rubber components of 100 mass parts, the amount that is derived from the zinc oxide of said masterbatch is 0.5～10 mass parts.
5. air bag as claimed in claim 1 is used rubber combination, it is characterized in that,
Based on the rubber components of 100 quality %, said rubber combination comprises the butyl rubber (B) of 90～100 quality % and the X 050 of 0～10 quality %.
6. air bag as claimed in claim 1 is used rubber combination, it is characterized in that,
Said masterbatch further comprises the cross-linked resin that is mixed in wherein.
7. air bag, it is by like each described rubber combination manufacturing in the claim 1～6.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010241398A JP5221623B2 (en) | 2010-10-27 | 2010-10-27 | Rubber composition for bladder and bladder |
| JP2010-241398 | 2010-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102453284A true CN102453284A (en) | 2012-05-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011102451030A Pending CN102453284A (en) | 2010-10-27 | 2011-08-16 | Rubber composition for bladder and bladder |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5221623B2 (en) |
| KR (1) | KR20120044255A (en) |
| CN (1) | CN102453284A (en) |
| BR (1) | BRPI1105885A2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731918A (en) * | 2012-07-20 | 2012-10-17 | 浙江华和塑胶科技有限公司 | Radial tyre bladder and preparation method thereof |
| CN104017280A (en) * | 2014-06-23 | 2014-09-03 | 东营金泰轮胎胶囊有限公司 | Process for producing ageing-resistant tire bladder sizing material |
| CN107250245A (en) * | 2015-02-05 | 2017-10-13 | 株式会社普利司通 | Rubber composition and its manufacture method, crosslinked rubber composition and tire |
| CN108690273A (en) * | 2017-04-04 | 2018-10-23 | 住友橡胶工业株式会社 | Curing bag rubber composition and curing bag |
| CN109957183A (en) * | 2019-03-12 | 2019-07-02 | 河南大林橡胶通信器材有限公司 | Diaphragm type clutch rubber pneumatic bag and preparation method thereof |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170101527A1 (en) * | 2014-03-26 | 2017-04-13 | Bridgestone Corporation | Rubber composition and tire |
| WO2016088817A1 (en) * | 2014-12-04 | 2016-06-09 | 横浜ゴム株式会社 | Rubber composition for tire-vulcanizing bladder, and tire-vulcanizing bladder produced using same |
| JP6488118B2 (en) * | 2014-12-17 | 2019-03-20 | 住友ゴム工業株式会社 | Rubber composition for bladder, method for producing the same, and bladder |
| KR20170133358A (en) * | 2015-03-30 | 2017-12-05 | 아란세오 네덜란즈 비.브이. | Curable rubber composition |
| WO2018008630A1 (en) * | 2016-07-04 | 2018-01-11 | 住友ゴム工業株式会社 | Rubber composition |
| JP6817043B2 (en) * | 2016-11-28 | 2021-01-20 | 松本油脂製薬株式会社 | Release agent for internal bladder and its use |
| JP2018193484A (en) * | 2017-05-18 | 2018-12-06 | 横浜ゴム株式会社 | Method for producing rubber composition for bladder |
| JP7225559B2 (en) * | 2018-04-24 | 2023-02-21 | 住友ゴム工業株式会社 | Bladder and tire inner components, and processing aids |
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| JPH1044258A (en) * | 1996-07-31 | 1998-02-17 | Bridgestone Corp | Manufacture of rubber article |
| JP4764014B2 (en) * | 2004-08-27 | 2011-08-31 | 株式会社ブリヂストン | Rubber composition and crosslinked rubber using the same |
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- 2010-10-27 JP JP2010241398A patent/JP5221623B2/en not_active Expired - Fee Related
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- 2011-08-16 CN CN2011102451030A patent/CN102453284A/en active Pending
- 2011-10-25 KR KR1020110109306A patent/KR20120044255A/en not_active Application Discontinuation
- 2011-10-26 BR BRPI1105885-4A patent/BRPI1105885A2/en not_active IP Right Cessation
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| CN1385473A (en) * | 2002-05-30 | 2002-12-18 | 骆天荣 | Modified nano zinc oxide compound mother granule for plastics and preparation method thereof |
| CN1388155A (en) * | 2002-06-03 | 2003-01-01 | 骆天荣 | Modified composite nano zinc oxide agglomerate as rubber additive and its prepn |
| JP2005075891A (en) * | 2003-08-29 | 2005-03-24 | Sumitomo Rubber Ind Ltd | Bladder formulation |
| JP2008101127A (en) * | 2006-10-19 | 2008-05-01 | Sumitomo Rubber Ind Ltd | Rubber composition and tire having tread using the same |
| CN101602866A (en) * | 2009-07-09 | 2009-12-16 | 四机赛瓦石油钻采设备有限公司 | A kind of cold-resistant rubber material of making by air bag and preparation method thereof that is suitable for |
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| CN102731918A (en) * | 2012-07-20 | 2012-10-17 | 浙江华和塑胶科技有限公司 | Radial tyre bladder and preparation method thereof |
| CN102731918B (en) * | 2012-07-20 | 2013-11-20 | 浙江华和塑胶科技有限公司 | Radial tyre bladder and preparation method thereof |
| CN104017280A (en) * | 2014-06-23 | 2014-09-03 | 东营金泰轮胎胶囊有限公司 | Process for producing ageing-resistant tire bladder sizing material |
| CN104017280B (en) * | 2014-06-23 | 2016-01-20 | 东营金泰轮胎胶囊有限公司 | The production technique of ageing-resistant tyre capsule sizing material |
| CN107250245A (en) * | 2015-02-05 | 2017-10-13 | 株式会社普利司通 | Rubber composition and its manufacture method, crosslinked rubber composition and tire |
| CN107250245B (en) * | 2015-02-05 | 2019-06-04 | 株式会社普利司通 | Rubber composition and its manufacturing method, crosslinked rubber composition and tire |
| US10336138B2 (en) | 2015-02-05 | 2019-07-02 | Bridgestone Corporation | Rubber composition and method for producing same, crosslinked rubber composition, and tire |
| CN108690273A (en) * | 2017-04-04 | 2018-10-23 | 住友橡胶工业株式会社 | Curing bag rubber composition and curing bag |
| CN109957183A (en) * | 2019-03-12 | 2019-07-02 | 河南大林橡胶通信器材有限公司 | Diaphragm type clutch rubber pneumatic bag and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| BRPI1105885A2 (en) | 2013-02-26 |
| JP2012092243A (en) | 2012-05-17 |
| JP5221623B2 (en) | 2013-06-26 |
| KR20120044255A (en) | 2012-05-07 |
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Application publication date: 20120516 |