CN107922665A - Rubber composition and cross-linked rubber article and its manufacture method - Google Patents
Rubber composition and cross-linked rubber article and its manufacture method Download PDFInfo
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- CN107922665A CN107922665A CN201680048011.4A CN201680048011A CN107922665A CN 107922665 A CN107922665 A CN 107922665A CN 201680048011 A CN201680048011 A CN 201680048011A CN 107922665 A CN107922665 A CN 107922665A
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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
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
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- Engineering & Computer Science (AREA)
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention relates to rubber composition, it contains rubber and the thermal expansivity micro-capsule of volumetric expansion is carried out by heating, it is characterized in that, relative to the rubber of 100 mass parts, the content of thermal expansivity micro-capsule is 1.5~10.7 mass parts, with 180 DEG C of temperature, the condition at 0.5 degree of vibration number 100cpm and amplitude angle is to comprising containing rubber, thermal expansivity micro-capsule, the test film of the uncrosslinked rubber composition of crosslinking agent and crosslinking accelerator is heat-treated and is made in the case that it carries out the volumetric expansion of cross-linking reaction and thermal expansivity micro-capsule, time t when test film is expanded to show maximum pressure due to heat treatment1With time t during optimal crosslinking points by 2 defineds of JIS K63002Time difference Δ t (=t2‑t1) it is 1.0~4.5 minutes.
Description
Technical field
Low-gravity cross-linked rubber article for being obtained the present invention relates to rubber composition and using the rubber composition and
Its manufacture method, the rubber composition contains rubber and the thermal expansivity micro-capsule of volumetric expansion is carried out by heating, described
Low-gravity cross-linked rubber article is the elastic rubber production of the crosslinked rubber composition comprising the fretting map state containing swelling bag
Product.
Background technology
In recent years, for environmental protection and raising fuel efficiency, it is desirable to mitigate the weight of the vehicles such as automobile, as one
Ring, structure member are also required to mitigate weight.For example, for automobile using rubber components, carrying out using thermal expansivity micro-capsule
The research of low-gravity.
In patent document 1, following weather strip is disclosed：High molecular material compositions is are extruded by it, molding sulfuration
And the weather strip formed, it is characterised in that just to only supporting at the sealing sealed using the gap of object of weather strip
For at least face side of socket part position, formed by high molecular material compositions, which is at least combined with
The ethylene/alpha-olefin/unconjugated polyene copolymer of 100phr, more than 50phr but in the arithmetic mean diameter of below 120phr
The carbon black of more than 60nm, the softening agent of below 100phr and thermal expansivity micro-capsule, on the surface of abutting portion formed with coming from
The male and fomale(M＆F) of thermal expansivity micro-capsule, while coming from the surface of the male and fomale(M＆F) of the thermal expansivity micro-capsule formed with coming from carbon
Rough surface.
In patent document, following rubber material composition and automobile using weather strip are disclosed：The elastomeric material combines
Thing is combined with the arithmetic mean diameter 60nm of the ethylene/alpha-olefin/unconjugated polyene copolymer of 100phr, 50phr~100phr
The organo-silicon compound and thermal expansivity that carbon black above, the softening agent of below 100phr, (25 DEG C) of viscosity are more than 1000cSt
Micro-capsule, the automobile using weather strip be said composition is extruded, molding sulfuration and the automobile using weather strip formed, in supporting for weather strip
For at least face side formed with the male and fomale(M＆F) for coming from carbon black, proportion is more than 0.3 in socket part position.
There is the manufacture method of the products formed of following weather strip etc. disclosed in patent document 3, the products formed contains bag
Matrix containing polymeric material and the multiple capsules being scattered in the matrix, and because of the expansion of capsule and on surface formed with bumps,
The manufacture method includes：Prepare with by expansion and the shell exposed division of capsule that exposes on the surface and by broken after expansion
Split and the sulfidization molding body of shell protrusion from the outwardly protruding capsule in surface, then carry out from the elimination of the surface of sulfidization molding body
The finishing processing of shell protrusion.
In addition, in patent document 4, following expanded moldings are disclosed:It is by micro- to being combined with thermal expansivity
The unvulcanized rubber material of capsule is vulcanized to be existed with the blown rubber formed body obtained from bubble space is internally formed, its feature
In, in the bubble space formed inside elastomeric material, make to produce the hole that internal gas passes through on the shell of thermal expansivity micro-capsule,
At least a portion between the inner face in bubble space and the shell of thermal expansivity micro-capsule is formed with gap；Record and be used as the foaming
The preferred weather strip of formed body.
Prior art literature
Patent document 1：Japanese Unexamined Patent Publication 2007-186559 publications
Patent document 2：Japanese Unexamined Patent Publication 2008-56748 publications
Patent document 3：Japanese Unexamined Patent Publication 2009-161587 publications
Patent document 4：Japanese Unexamined Patent Publication 2011-256223 publications
The content of the invention
The subject that the invention solves
Formed body in above patent document 1~4 is respectively provided with includes swelling bag in the inner dispersion for vulcanizing rubber mass
Structure, therefore although realize low-gravity, but be hardened in the presence of only superficial layer, the problem of rough surface occur.
The subject of the invention is to provide rubber composition and cross-linked rubber article and its manufacture method, the rubber group
Compound is the elastic rubber product of the crosslinked rubber composition comprising the fretting map state containing swelling bag and can be produced with height
Rate and expeditiously manufacture proportion crosslinking rubber system as low as excellent less than the aesthetic appearance that 1.00, rough surface etc. is inhibited
Product.
The means to solve the problem
The inventors of the present invention carry out injection molding, the uncrosslinked rubber composition by using uncrosslinked rubber composition
Carrying out following experiments：Using the condition of 0.5 degree of 180 DEG C of temperature, frequency (vibration frequency) 100cpm and amplitude angle, to containing rubber
Glue, be heat-treated by heating to carry out the test film of the thermal expansivity micro-capsule of volumetric expansion and crosslinking agent, so that it is carried out
In the case of the volumetric expansion of cross-linking reaction and thermal expansivity micro-capsule, test film is expanded due to heat treatment to show maximum pressure
When time t1With JIS K6300-2 as defined in optimal crosslinking points when time t2Time difference Δ t (=t2-t1) for 1.0~
4.5 minutes, as a result, can high efficient production have fretting map state, the proportion as low as small than what the chamber of mould somewhat expanded
In the cross-linked rubber article that the aesthetic appearance that 1.00, rough surface etc. is inhibited is excellent, the present invention is completed.It should illustrate that institute
Call fretting map state, refer to the volume reference relative to uncrosslinked rubber composition of crosslinked rubber composition expansion rate it is upper
Limit is 15%.
The present invention is shown in following.
1. rubber composition, it is characterised in that it is to carry out the thermal expansion of volumetric expansion containing rubber and by heating
Property micro-capsule,
It is 1.5~10.7 matter relative to the above-mentioned rubber of 100 mass parts for the content of above-mentioned thermal expansivity micro-capsule
Measure part,
Carry out with the condition of 0.5 degree of 180 DEG C of temperature, frequency 100cpm and amplitude angle to comprising containing above-mentioned rubber, on
The uncrosslinked test film for stating the rubber composition of thermal expansivity micro-capsule and crosslinking agent is heat-treated and it is carried out cross-linking reaction
In the case of experiment with the volumetric expansion of the thermal expansivity micro-capsule, above-mentioned test film expanded due to heat treatment it is shown most
Time t during big pressure1With the time t as defined in JIS K6300-2 during optimal crosslinking points2Time difference Δ t (=t2-t1)
For 1.0~4.5 minutes.
2. the rubber composition described in above-mentioned 1, wherein, the maximum swelling temperature of above-mentioned thermal expansivity micro-capsule for 140 DEG C with
On.
3. the rubber composition described in above-mentioned 1 or 2, wherein, the particle diameter of above-mentioned thermal expansivity micro-capsule is 18~50 μm.
4. above-mentioned 1~3 any one of them rubber composition, wherein, for above-mentioned thermal expansivity micro-capsule, comprising
Contain liquid compound in the inside of the shell of thermoplastic resin material.
5. above-mentioned 1~4 any one of them rubber composition, wherein, above-mentioned rubber includes ethene-alpha-olefin system rubber
Glue.
6. above-mentioned 1~5 any one of them rubber composition, it also contains crosslinking agent.
7. above-mentioned 1~6 any one of them rubber composition, it is used for injection molding.
8. the rubber composition described in above-mentioned 6 or 7, it is to make for 2~5 minutes the deadline for making the cross-linking reaction
Rubber composition.
9. use the cross-linked rubber article made by the rubber composition described in above-mentioned 6.
10. the cross-linked rubber article described in above-mentioned 9, it is the harness lantern ring (grommet) or rubber bushing (bush).
11. the manufacture method of cross-linked rubber article, it is characterised in that possess and carry out the rubber composition described in above-mentioned 6
The process of injection molding.
Invention effect
Rubber composition according to the present invention, is suitable for：In the presence of a crosslinking agent, by using the shaping side of heat treatment
Method, makes thermal expansivity micro-capsule expand and be formed as fretting map state, and manufacture proportion is as low as less than 1.00, rough surface etc. and is pressed down
The excellent cross-linked rubber article of the aesthetic appearance of system.
The manufacture method of rubber composition according to the present invention, it is as low as small can to obtain proportion with high production rate and high efficiency
In the cross-linked rubber article of the excellent fretting map state of the aesthetic appearance that 1.00, rough surface etc. is inhibited.In addition, therefore use
Rubber composition with special properties, can carry out the crosslinking rubber small as the deviation of proportion for entirety in a short time
A large amount of manufactures of product.Thus, it is suitable for use with the continuous manufacture of injection molding etc..
Brief description of the drawings
[Fig. 1] is to show time t of the present invention1And t2Definite method skeleton diagram.
[Fig. 2] is the outline of the cableties (cord bush) for an example for being shown as the cross-linked rubber article of the present invention
Figure.
[Fig. 3] is using the article with harness integrated as the lantern ring of other examples of the cross-linked rubber article of the present invention
Summary section.
[Fig. 4] is the summary section of the manufacture method for the integrated article for showing Fig. 3.
Embodiment
1. rubber composition
The rubber composition of the present invention is to contain rubber with specific ratio and the heat of volumetric expansion is carried out by heating
The uncrosslinked composition of dilatancy micro-capsule, is suitable for：Coordinate crosslinking agent and use injection moulding machine, extruder, compressor, roller etc.
Known forming method, particularly preferred injection molding forming method manufacture cross-linked rubber article.
1-1. rubber
The component can preferably vulcanize or the uncrosslinked rubber of peroxide crosslinking, such as natural rubber, fourth can be used
Diene rubber, the butadiene rubber containing syndyotactic 1,2- polybutadiene (SPB), the natural rubber containing SPB, isoprene rubber
The polymer of the diene monomer of glue, butyl rubber, neoprene etc.；Acrylonitrile-butadiene rubber, NCR nitrile chloroprene rubber, nitrile
The acrylonitrile of base isoprene rubber etc.-diene copolymer rubber；SBR styrene butadiene rubbers, styrene-neoprene, benzene second
The styrenic-diene copolymer rubber of alkene-isoprene rubber etc.；Ethene-alpha-olefin copolymer rubber, ethene-alpha-olefin-diene are common
Ethene-alpha-olefin system rubber of poly- rubber etc. etc..Wherein, optimal ethylene-alpha-olefin system rubber, from resistance in cross-linked rubber article
From the viewpoint of hot and weatherability, particularly preferred ethene-alpha-olefin-diene copolymer rubber.
Above-mentioned ethene-alpha-olefin-diene copolymer rubber is the terpolymer that ethene, alpha-olefin and diene are copolymerized.
As above-mentioned alpha-olefin, can enumerate propylene, 1- butylene, 2- butylene, 1- amylenes, 1- hexenes, 4-methyl-1-pentene,
1- heptene, 5- methyl isophthalic acids-hexene, 1- octenes, 1- nonenes, 5- ethyl -1- hexenes, 1- decene, 1- dodecylenes, 3- methyl isophthalic acids -
Butylene etc., wherein, preferably carbon number is 3~5 compound.
Above-mentioned diene is preferably non-conjugated diene, for example, can enumerate Isosorbide-5-Nitrae-pentadiene, Isosorbide-5-Nitrae-hexadiene, 1,5- hexadienes,
1,7- octadienes, 1,9- decadinene, 3,6- dimethyl -1,7- octadienes, 4,5- dimethyl -1,7- octadienes, 5- methyl isophthalic acids, 8-
Nonadiene, bicyclopentadiene, 5- ethylidene -2- norbornene, 5- vinyl -2- norbornene, 2,5- norbornadienes etc..Its
In, preferred 5- ethylidene -2- norbornene.
With regard to forming the ethylene unit of above-mentioned ethene-alpha-olefin-diene copolymer rubber, coming from the unit of alpha-olefin and come from
For the content ratio of the unit of diene, with they add up to 100 mass % in the case of, respectively preferably 50~70 matter
Measure %, 25~50 mass % and 1~15 mass %, more preferably 55~65 mass %, 30~45 mass % and 5~12 mass %.
The rubber composition of the present invention can contain only a kind of above-mentioned rubber, can also contain two or more above-mentioned rubber.
1-2. thermal expansivity micro-capsules
For the component, increase preferably by heating possessive volume internal substance (for gas or solid or
Liquid and by heating and the material that gasifies) be sealing into the grain of inside comprising resin material or by its shell formed
Shape micro-capsule.
The thermal expansivity micro-capsule be by be heated to preferably more than 135 DEG C, more preferably more than 140 DEG C, further preferred 160
~185 DEG C, particularly preferably 170~185 DEG C and carry out the micro-capsule of volumetric expansion.Above-mentioned temperature is generally referred to as " expanding
Beginning temperature ".In addition, the maximum swelling temperature of above-mentioned thermal expansivity micro-capsule is preferably more than 140 DEG C, more preferably 145 DEG C~200
DEG C, particularly preferably 150 DEG C~180 DEG C.If the thermal expansivity micro-capsule with such property is heated, internal substance carries out
Volumetric expansion, the resin material softening for forming shell, therefore obtain the capsule (swelling bag) expanded because of internal pressure.The present invention
In, above-mentioned thermal expansivity micro-capsule is more preferably in inside comprising resin material (resin combination) or by its shell formed
Containing liquids compound.
Liquid compound as the internal substance of above-mentioned composition thermal expansivity micro-capsule, which preferably has, forms above-mentioned thermal expansion
Property micro-capsule shell resin material softening temperature below boiling point (atmospheric pressure), such as may be selected：Normal butane, isobutyl
Alkane, cyclobutane, pentane, isopentane, pentamethylene, n-hexane, 2- methylpentanes, 2,2- dimethylbutanes, hexamethylene, positive heptan
The hydrocarbon of alkane, cycloheptane, normal octane, cyclooctane etc.；C3F7OCH3、C4F9OCH3、C4F9OC2H5Deng Hydrofluoroether compounds etc..It is above-mentioned
Liquid compound can only be a kind or two or more.As aforesaid liquid compound, preferred hydrocarbons, particularly preferably include
Carbon number is 4~5 low boiling hydrocarbon.In addition, the resin material for forming shell preferably has thermoplasticity, thermoplasticity is preferably comprised
Compound, the thermoplastic compound, which includes, to be come from selected from acrylonitrile, methacrylonitrile, alkyl acrylate, metering system
Acid alkyl ester, vinyl chloride, vinylidene chloride, vinyl acetate, aromatic ethenyl compound, acrylic acid, methacrylic acid, Malaysia
Acid, fumaric acid, itaconic acid, citraconic acid, acrylamide, substituted acrylamide, Methacrylamide, substituent methyl acrylamide and
At least one kind of construction unit in multi-functional compounds with more than 2 polymerism carbon-to-carbon unsaturated bonds.As the heat
Plastic resin, such as Vingon can be enumerated；The acrylic (common) of vinylidene chloride-acrylonitrile copolymer, polyacrylonitrile etc.
Polymer；The acrylic acid series (co) polymer of polymethyl methacrylate etc.；Polyvinyl chloride etc..Wherein, particularly preferred acrylonitrile
It is (co) polymer.Above-mentioned resin material (resin combination) can contain stabilizer, ultra-violet absorber, antioxidant, anti-quiet
The additive of electric agent, fire retardant etc..
The shape of above-mentioned thermal expansivity micro-capsule is spherical or oval spherical, from giving appropriate expansion rate, give with good
From the viewpoint of the cross-linked rubber article of good epidermis, the particle diameter that is measured by thermo-mechanical analysis (TMA) etc. be preferably 17 μm with
On, more preferably 18~50 μm.
The rubber composition of the present invention can contain only a kind of above-mentioned thermal expansivity micro-capsule, can also contain two or more above-mentioned thermal expansivity
Micro-capsule.
For the content of thermal expansivity micro-capsule contained in the rubber composition in the present invention, from obtained crosslinking rubber
From the viewpoint of the proportion and intensity of composition, in the case of using the content of above-mentioned rubber as 100 mass parts, be 1.5~
10.7 mass parts, are preferably 1.8~10.5 mass parts, more preferably 2.0~10.2 mass parts.
1-3. other compositions
For the rubber composition of the present invention, property (wearability, electric conductivity according to required by cross-linked rubber article
Deng) etc., also contain as being helped as the crosslinking agent of known compounding agent, crosslinking accelerator, organic foaming agent, processing in the past
Agent, filler, softening agent, age resister, lubricant, fire retardant, stabilizer, antistatic additive, fungi-proofing/mould inhibitor, sliding promote
Into agent, colouring agent etc..
As above-mentioned crosslinking agent, sulphur can be enumerated；Halogenation sulphur；Organic peroxide etc..
As above-mentioned sulphur, powder sulphur, precipitated sulfur, colloid sulphur, insoluble sulfur, polymolecularity sulphur etc. can be enumerated.In addition, conduct
Above-mentioned halogenation sulphur, can enumerate sulfur monochloride, sulfur dichloride etc..
In addition, as above-mentioned organic peroxide, benzoyl peroxide, 1,1- bis(t-butylperoxy) -3 can be enumerated,
3,5- trimethyl-cyclohexanes, 2,5- dimethyl -2,5- two (benzoylperoxy) hexane, two (t-butylperoxy) diisopropyls
Benzene, 1,4- double [(tert-butyl group) peroxy isopropyl] benzene, two (t-butylperoxy) benzoic ethers, the tertiary fourths of perbenzoic acid
Ester, dicumyl peroxide, t-butylcumyl peroxide, 2,5- dimethyl -2,5- bis- (t-butylperoxy) hexane, peroxidating two
The tert-butyl group, 2,5- dimethyl -2,5- two (t-butylperoxy) -3- hexenes etc..
The rubber composition of the present invention can only include a kind of above-mentioned crosslinking agent, can also include two or more.
In the case where the rubber composition of the present invention contains crosslinking agent, for its content, from the viewpoint of crosslinking rate
Consider, when using the content of above-mentioned rubber as 100 mass parts, preferably 0.2~10 mass parts, more preferably 0.4~8 mass parts, into
One step preferably 0.5~6 mass parts.
As above-mentioned crosslinking accelerator, N- cyclohexyl -2-[4-morpholinodithio base sulfenamide, the N- tert-butyl group -2- benzene can be enumerated
Benzothiazolyl sulfenamide, N- oxydiethylenes -2-[4-morpholinodithio base sulfenamide, N- oxydiethylene -2- benzo thiophenes
The sulfenamide based compound of oxazolyl sulfenamide, N, N'- diisopropyls -2-[4-morpholinodithio base sulfenamide etc.；Dimethyl two
Thiocarbamic acid sodium, zinc dimethyl dithiocarbamate, zinc diethyl dithiocarbamate, dibutyl dithio amino
Zinc formate, zinc-ethylphenyl dithiocarbamate, N- zinc pentamethylene dithiocarbamates, dibenzyl dithio amino first
The aminodithioformic acid based compound of sour zinc etc.；Tetramethylthiuram monosulfide, a tetraethylthiuram sulfide, a vulcanization four
Isopropyl thiuram, TBTM tetrabutyl thiuram monosulfide, a vulcanization tetra-benzyl thiram, tetramethylthiuram disulfide, curing
Thiuram, tetraisopropylthiuram disulfide, tetrabutylthiuram disulfide, tetra-benzyl thiram disulfide, two sulphur
Change the thiuram based compound of four (2- ethylhexyls) thiurams etc.；2-mercaptobenzothiazole, the base curing of two -2-[4-morpholinodithio
Thing, 2- (4'- morpholinoes two are thio) benzothiazole, the zinc salt of 2-mercaptobenzothiazole, the cyclohexylamine salt of 2-mercaptobenzothiazole
Deng thiazole compound；The guanidine based compound of 1,3- diphenylguanidines, 1,3- di-o-tolyl guanidines, 1- OTBG o tolylbiguanides etc.；
The thiocarbamide based compound of diethyl thiourea etc.；The xanthan of sodium isopropyl xanthate, zinc isopropyl xanthate, zinc butyl xanthate etc.
Sour based compound；Metering system acid metal salt of magnesium dimethacrylate, zinc dimethacrylate etc. etc..
The rubber composition of the present invention can contain only a kind of above-mentioned crosslinking accelerator, can also contain two or more above-mentioned crosslinking and promote
Agent.In the present invention, above-mentioned crosslinking accelerator preferably comprises sulfenamide based compound, the particularly preferred sulfenamide system chemical combination
The combination of other crosslinking agents of thing and thiuram based compound, aminodithioformic acid based compound etc..
In the case where the rubber composition of the present invention contains crosslinking accelerator, for its content, from coking stability
And it is preferably 1~10 mass parts, more preferably when using the content of above-mentioned rubber as 100 mass parts from the viewpoint of crosslinking rate
For 1.5~8 mass parts, more preferably 2~6 mass parts.
Sulfenamide based compound and thiuram based compound, aminodithioformic acid system are included in above-mentioned crosslinking accelerator
In the case of other crosslinking agents of compound etc., the preferable content ratio of sulfenamide based compound and other crosslinking agents is such as
Under.For the content of other crosslinking agents, in the case of using the content of sulfenamide based compound as 100 mass parts, preferably
It is below mass part for 120, more preferably 5~110 mass parts, more preferably 55~105 mass parts.
As above-mentioned organic foaming agent, 4,4'- oxos double (benzene sulfonyl hydrazide), azodicarbonamide, dinitrosos can be enumerated
Pentamethylene tetramine, azobis isobutyronitrile, unifor, hydrazo-dicarbonamide (hydrazodicarbonamide),
Barium azodicarboxylate etc..
In the case where the rubber composition of the present invention contains organic foaming agent, for the upper limit of its content, from offer
It is excellent in the case of using the content of above-mentioned rubber as 100 mass parts from the viewpoint of cross-linked rubber article with good epidermis
Elect 1.0 mass parts as, more preferably 0.7 mass parts, more preferably 0.5 mass parts.
As above-mentioned processing aid, zinc oxide can be enumerated；The advanced fat of castor oil acid, stearic acid, palmitic acid, laurate etc.
Fat acid；The salt of the higher fatty acids of barium stearate, zinc stearate, calcium stearate etc.；Castor oil acid, stearic acid, palmitic acid, bay
Esters of the higher fatty acids of acid etc. etc..
As above-mentioned filler, can enumerate carbon black, cornstarch, calcium carbonate, clay, talcum, diatomite, silica,
Aluminium oxide, aluminum sulfate, barium sulfate, calcium sulfate, basic magnesium carbonate, aluminium hydroxide etc..
As above-mentioned softening agent, the petroleum line softener of processing oil, lubricating oil, paraffin, vaseline etc. can be enumerated；Castor-oil plant
The fatty oil softener of oil, Linseed oil, rapeseed oil, coconut oil etc.；Tall oil；Ointment；Beeswax, Brazil wax, wool
The wax class of fat etc.；The aliphatic acid or soap of castor oil acid, palmitic acid, barium stearate, calcium stearate, zinc laurate etc.；Stone
Synthesis macromolecule of oleoresin, random polypropylene, coumarone-indene resin etc. etc..
As above-mentioned age resister, can enumerate naphthylamines based compound, hexichol amine compound, p-phenylenediamine based compound,
Quinoline based compound, hydroquinone derivatives, single phenol based compound, thiobisphenol based compound, hindered phenol compound, phosphite ester system
Compound etc..
As above-mentioned lubricant, solid paraffin, atoleine, paraffin series synthetic wax, Tissuemat E, stearic acid can be enumerated
Zinc, hydroxy stearic acid, fatty acid amide, fatty acid ester, silicon gel, silicone oil, organosilicon powder, the polymerization containing organosilicon
Thing, organosilicon graft polymers etc..
In the present invention, in the presence of a crosslinking agent, there is provided the preferable rubber composition of excellent cross-linked rubber article
For containing:The rubber and maximum swelling temperature of the rubber of system containing ethene-alpha-olefin are 140 DEG C~175 DEG C of thermal expansivity micro-capsule
Composition.The crosslinking agent used is preferably the crosslinking agent comprising sulfenamide based compound and thiuram based compound.
The manufacture method of 1-4. rubber compositions
The rubber composition of the present invention can conventionally mix each component to manufacture.
Preferable manufacture method is the method for possessing successively following process：Will be except thermal expansivity micro-capsule, crosslinking agent and friendship
Join the process (the 1st compounding procedure) of the compounding agent and compounding rubber beyond accelerating agent；By obtained mixture (hereinafter referred to as
" the 1st mixture "), thermal expansivity micro-capsule, crosslinking agent, process (the mixing work of crosslinking accelerator and the mixing of other compounding agent
Sequence).
In above-mentioned 1st compounding procedure, it can be used such as Banbury mixer, mixer, kneader.
In above-mentioned mixed processes, thermal expansivity micro-capsule, crosslinking agent and crosslinking accelerator are coordinated into the 1st mixture, such as
Using open roller etc., preferably specific thermic dilatation micro-capsule low more than 20 DEG C of expansion starting temperature temperature, more preferably 100
Below DEG C, further preferably it is kneaded in 60 DEG C~90 DEG C, the temperature particularly preferably at 70 DEG C~80 DEG C.What is used at this time is upper
It is preferably it is reduced to less than 50 DEG C to state the 1st mixture.Incorporation time in above-mentioned mixed processes is typically 30 seconds~10 points
Clock.
The performance of 1-5. rubber compositions
In the present invention, the rubber group for the cross-linked rubber article that proportion is low, rough surface is inhibited, aesthetic appearance is excellent is formed
Compound is the rubber composition for having following properties：Contain rubber, thermal expansivity micro-capsule using by the way that the above method is prepared
Test film (uncrosslinked test film) is made with the composition of crosslinking agent (following, to be referred to as " composition (A) "), to the experiment
Piece be heat-treated under conditions of 0.5 degree of 180 DEG C of temperature, frequency (vibration frequency) 100cpm and amplitude angle making its progress
The experiment of the volumetric expansion of cross-linking reaction and thermal expansivity micro-capsule, to form crosslinked rubber composition, at this time, the test film by
Time t when heat treatment is expanded to show maximum pressure1With optimal crosslinking points (the optimal sulphur as defined in JIS K6300-2
Change point) when time t2Time difference Δ t (=t2-t1) be 1.0~4.5 minutes, preferably 1.5~3.5 minutes, more preferably 2.0~
2.7 minute.
With regard to the thermal expansivity micro-capsule and the content ratio of crosslinking agent included in above-mentioned composition (A), relative to 100 mass parts
Rubber, is respectively preferably 1.5~10.7 mass parts and 0.2~10 mass parts.
In the situation of above-mentioned composition (A) containing crosslinking accelerator, for the content ratio of the crosslinking accelerator, relatively
In 100 mass parts rubber be preferably 1~10 mass parts.As the crosslinking accelerator, foregoing illustrative component can be used.Using
The situation of two or more crosslinking accelerator, preferably sulfenamide based compound and thiuram based compound, aminodithioformic acid system
Other crosslinking agents of compound etc. are used in combination, and use ratio is also as described above.
For above-mentioned experiment, can be used can carry out using the device of the method based on JIS K6300-2, time t1
And t2Determined based on curve shown in Fig. 1.1st axis represents the turgor pressure of the uncrosslinked test film formed by above-mentioned composition (A)
Power.If starting to be heat-treated, cross-linking reaction is with regard to slowly carrying out, and at its initial stage, thermal expansivity micro-capsule is expanded.Then, exist
Time t1Under, after the pressure that is applied on test film reaches maximum, the outer casing rupture of a part of swelling bag or melting, but formed by
The crosslinked rubber composition of fretting map state caused by swelling bag, the bulbs of pressure stabilize.On the other hand, the 2nd axis represents to hand over
Join the moment of torsion of rubber composition, in general drawn curve is referred to as " curing curve ".By the curing curve, can obtain by
Optimal crosslinking points (optimum cure point) as defined in JIS K 6300-2, i.e. to be crosslinked peak torque (maximum vulcanization moment of torsion) THWith
It is crosslinked minimal torque (vulcanization minimal torque) TLDifference TEFor 100% when, obtain TEBe worth for 90% (it is 90% that crosslinking, which carries out rate) when
Time (tc90), as time t2.By obtained t1And t2Above-mentioned Δ t can be calculated.
The productivity of the cross-linked rubber article of the rubber composition of the present invention is excellent, such as can be 6 by injection molding
Cross-linked rubber article is manufactured in minute, in preferably 5 minutes.Thus, rubber composition of the invention is suitable for cross-linked rubber article
A large amount of productions.
1-6. crosslinked rubber composition
By by the rubber composition containing crosslinking agent for pressurized, heated, steam heating, baking oven heating, Hot-blast Heating etc.
Known heating means or forming method (aftermentioned), crosslinked rubber composition can be formed.
By by above-mentioned rubber composition high more than 5 DEG C of the expansion starting temperature of specific thermic dilatation micro-capsule temperature, more
It is preferred that 5 DEG C high~30 DEG C, further preferably 10 DEG C high~20 DEG C of temperature heated, crosslinking agent plays a role, and rubber is subject to
It is three-dimensional cross-linked.In addition, thermal expansivity micro-capsule expands and forms swelling bag, which is comprised in by with 3 with dispersity
In the matrix of crosslinking rubber composition for tieing up cross-linked structure.Thus, the crosslinking rubber with the fretting map state of excellent resilience can be obtained
Glue composition.It is explained, in the crosslinked rubber composition of the present invention, a part of thermal expansivity micro-capsule is broken upon inflation sometimes
Split, but most of swelling bag with substantially homogeneous size by comprising.Contain in the rubber composition of raw material beyond crosslinking agent
In the case of other compounding agents, which is also dispersed in the matrix being made of the crosslinking rubber with 3-dimensional cross-linked structure.
The average grain diameter of above-mentioned swelling bag is preferably 18~50 μm.
The proportion of above-mentioned crosslinked rubber composition is preferably smaller than 1.00, more preferably 0.92 (according to JIS K 6268A methods)~
0.99, further preferred 0.96~0.99.
2. cross-linked rubber article
The cross-linked rubber article of the present invention is to use to prepare containing the rubber composition of crosslinking agent, by containing swelling bag
Fretting map state the elastic rubber product that is formed of crosslinked rubber composition.The shape of the cross-linked rubber article of the present invention can
Depending on purpose, purposes etc..The shape of cross-linked rubber article can be made into the simple shape of plate body, barred body, cylinder etc., or tool
There is the complicated shape of through hole, bumps, curved surface, thinner wall section, heavy section etc..For the cross-linked rubber article of the present invention, due to
Using the rubber composition of the invention described above as manufacture raw material, therefore using injection moulding machine, extruder, compressor, roller etc.
In the case of, it is the low-gravity cross-linked rubber article that rough surface etc. is inhibited, aesthetic appearance is excellent, there is smooth epidermis.
As the cross-linked rubber article of the present invention, rubber bushing, the lantern ring, weather strip, the glass run of cableties etc. can be enumerated
(glass run), side filler rod, smooth assembling (flash mount molding), sealing material etc..Wherein, preferable mode is rubber
Glue bushing and the lantern ring.
Above-mentioned rubber bushing is to be disposed in the component that component is clamped or fixed each other or by wire-like members etc..Fig. 2
The cableties 10 for illustrating tubular are used as rubber bushing, and (a) is plan (top view), and (b) is profile (profilograph), and (c) is
Side view (line insertion section side).
For the cableties 10 of Fig. 2, side possesses the line insertion section 14 of the line insertion of holding at one end, has in another side
Standby line maintaining part 18, the line maintaining part 18 from the line that 14 side of line insertion section is inserted into will pass through the elastic and online outer of itself
The mode of side face connection carries out elastic deformation.In addition, in the inner peripheral surface of cableties 10, possesses valve portion 16, the valve portion 16 is with by line
14 side of insertion section and 18 side of line maintaining part carry out closed separation while the elastic online periphery that the line being inserted into is passed through itself
The mode of face connection improves line retentivity to carry out elastic deformation.It is explained, for the line maintaining part 18 of Fig. 2, sets
For the flange part 12 with rounding.
The above-mentioned lantern ring is endless member opening portion, having through hole for being embedded in object.Fig. 3 is to illustrate the lantern ring 24
Summary section, the lantern ring 24 make the peripheral part of large-diameter circular canister portion 28 be inscribed in institute's shape on the panel not illustrated
Into opening portion and be embedded with harness 22 in through hole.In Fig. 3, the integral compound being made of harness portion 22 and the lantern ring 24 is shown
Product 20.
3. the manufacture method of cross-linked rubber article
For manufacturing the method for above-mentioned cross-linked rubber article, it is not specifically limited, may be selected using injection moulding machine, squeezes
Go out the method for machine, compressor, roller etc..It is in particular with the method that can be carried out continuously the injection moulding machine largely manufactured the short time
Suitably, the present invention in cross-linked rubber article manufacture method possess by the rubber composition of the invention containing crosslinking agent into
The process of row injection molding.
, can be swollen according to the species of rubber, heat for the processing temperature of rubber composition when manufacturing cross-linked rubber article
Expansion starting temperature of swollen property micro-capsule etc. suitably selects, but is inhibited consideration from the rough surface of cross-linked rubber article, excellent
Select high more than 5 DEG C of the expansion starting temperature of specific thermic dilatation micro-capsule temperature, more preferably it is 5 DEG C high~30 DEG C, further preferably high
10 DEG C~20 DEG C of temperature.In addition, heating time (deadline of cross-linking reaction) is preferably 2~5 minutes, more preferably 2~3.5
Minute.That is, the molding time in injection molding processes is preferably 1~6 minute, more preferably 2~5 minutes, more preferably 2
~3.5 minutes.
In the present invention, by injection molding processes, it can obtain that surface is smooth and the cross-linked rubber article of excellent appearance, but
For the manufacturing method of the present invention, can possess as needed after injection molding processes to the surface of products formed or end not
Part is needed to carry out finishing step for removing etc. etc..
Hereinafter, for manufacturing the side of the integrated article 20 of harness 22 and the lantern ring 24 shown in Fig. 3 using injection molding
Method, is illustrated using Fig. 4.
Fig. 4 is the summary section for the die injection moulding 30 for possessing the 1st mould 32 and the 2nd mould 34, is configuration harness 22
And form the figure of mould closure state.Configuring remaining space segment in the mould after harness 22 becomes the chamber 38 of the lantern ring 24.
First, make the temperature of injection forming mold 30 more than 5 DEG C high for the expansion starting temperature of specific thermic dilatation micro-capsule
Temperature, more preferably 10 DEG C high~20 DEG C of temperature, the raw material entrance hole 36 from the top for being formed in the 1st mould 32, supply are heated
To the rubber composition of 100 DEG C~120 DEG C of flow regime, full of chamber 38.Then the state is preferably remained 1~6 minute,
More preferably keep 2~5 minutes, further preferably kept for 2~3 minutes.Then, the temperature for making die injection moulding 30 is 160
DEG C~185 DEG C after, open mould, the integrated article 20 being made of harness portion 22 and collar portion 24 is discharged.
For the collar portion 24 in obtained integrated article 20, due to comprising swelling bag, being in fretting map shape
State, size become bigger than above-mentioned chamber 38.The expansion rate of volume reference is typically 5~10%.
Embodiment
Hereinafter, embodiment is enumerated to the present invention to illustrate, but the present invention is from any restrictions of these embodiments.Should
Explanation is given, " part " below is quality criteria, unless otherwise indicated.
1. the manufacture and evaluation of rubber composition
1-1. material composition
The material composition used in the manufacture of rubber composition is as follows.
1-1-1. rubber
Use JSR company systems EPDM " EP57F " (trade name).
1-1-2. thermal expansivity micro-capsules
(1)M1
Dilatancy micro-capsule " マ Star モ ト マ イ Network ロ ス Off ェ ア-FN-78D " (business is heated using Song Ben greases drugmaker
The name of an article).Expansion starting temperature is 100 DEG C~120 DEG C, and maximum swelling temperature is 150 DEG C~165 DEG C, and particle diameter is 35~50 μm.
(2)M2
Use ponding chemical industrial company heat-expandable microsphere " ADVANCELL EMH204 " (trade name).Expansion starts
Temperature is 115 DEG C~125 DEG C, and maximum swelling temperature is 165 DEG C~175 DEG C, and particle diameter is 38~44 μm.
(M3)
Use ponding chemical industrial company heat-expandable microsphere " ADVANCELL EMH302 " (trade name).Expansion starts
Temperature is 130 DEG C~140 DEG C, and maximum swelling temperature is 160 DEG C~170 DEG C, and particle diameter is 18~24 μm.
(4)M4
Use Song Ben greases drugmaker heating dilatancy micro-capsule " マ Star モ ト マ イ Network ロ ス Off ェ ア-FN-180D "
(trade name).Expansion starting temperature is 140 DEG C~155 DEG C, and maximum swelling temperature is 175 DEG C~185 DEG C, and particle diameter is 35~45 μ
m。
1-1-3. crosslinking agent
Use He Jian chemical industrial companies sulphur " Jinhua print micro mist Sulfur 200mesh " (trade name).
1-1-4. crosslinking accelerator
(1)A1
Use the emerging chemical industrial company's N cyclohexyl 2 benzothiazole sulfenamide of imperial palace " ノ Network セ ラ-CZ-G "
(trade name).
(2)A2
Use the emerging chemical industrial company's tetramethyl thiuram disulfide of imperial palace " ノ Network セ ラ-TT-P " (commodity
Name).
(3)A3
Use the emerging chemical industrial company's Thiuram disulphide of imperial palace " ノ Network セ ラ-TT-G " (commodity
Name).
(4)A4
Use the emerging chemical industrial company's zinc dibutyl dithiocarbamate of imperial palace " ノ Network セ ラ-BZ-P " (commodity
Name).
(5)A5
Use the emerging chemical industrial company's zinc dimethyl dithiocarbamate of imperial palace " ノ Network セ ラ-PZ " (commodity
Name).
1-1-5. organic foaming agent
Use double (benzene sulfonyl hydrazide) " ネ オ セ Le ボ Application the N#1000S " (commodity of Yonghe County's chemical conversion industry company system 4,4'- oxos
Name).
1-1-6. filler
(1)F1
Use Xu カ ー ボ Application Block ラ ッ Network company systems carbon blacks " rising sun #60 " (trade name).
(2)F2
Use ball tail カ Le シ ウ system company system calcium carbonate " ス ー パ ー SS " (trade name).
1-1-7. softening agent
Use emerging production company system processing oil " the Off ッ コ ー Le プ ロ セ ス P400 " (trade name) of Fuji.
1-1-8. lubricant
Shi Yong East レ ダ ウ コ ー ニ Application グ シ リ コ ー Application company system super high molecular weight siloxane polymers " BY27-
002 " (trade name).
The manufacture method of 1-2. rubber compositions and evaluation
Embodiment 1-1~1-10 and comparative example 1-1~1-4
Above-mentioned raw materials component is used according to the amount ratio shown in table 1, manufacture rubber composition C1 is got according to following
~C14.
Using Kobe Steel's company system kneading machine " 1.7L MIXTRON BB ミ キ サ " (trade name), in 100 DEG C of temperature and
By compounding rubber under conditions of rotating speed 60rpm, then, put into addition to thermal expansivity micro-capsule, crosslinking agent and crosslinking accelerator
Compounding agent, continue to be kneaded under conditions of same as described above.Then, the mixing mill machine manufactured using Northwest ロ ー Le company,
Further it is kneaded under conditions of temperature 50 C, front side rotating speed 22rpm and rear side rotating speed 20rpm, modulates the 1st mixture.
Then, with above-mentioned the same terms, using the mixing mill machine of Northwest ロ ー Le company manufacture, the above-mentioned 1st is mixed
Refining thing, thermal expansivity micro-capsule, crosslinking agent and crosslinking accelerator are kneaded, and obtain the piece formed by uncrosslinked rubber composition
Material.
Then, machining is carried out to the sheet material and forms 5 grams of test film, use Alpha Technologies companies
The rubber process analyzer " RPA2000 " (model name) of manufacture, carries out crosslinking assays.Determination condition is 180 DEG C of temperature, frequency
0.5 degree of (vibration frequency) 100cpm and amplitude angle.Chart as shown in Figure 1 is obtained by the measure, is asked by computer disposal
Go out t1And t2, further pass through formula：Δ t=t2-t1And obtain Δ t (referring to table 1).
In addition, using rubber composition as moulding material, the heating pressue device " 37T that is manufactured using Yan Cheng industrial groups
プ レ ス " (trade name), are processed under conditions of 180 DEG C of temperature and pressure 16MPa, obtain the crosslinking sheet rubber of thick 2mm
Material.Then, the crosslinking rubber sheet is visually observed, judges to be led with the presence or absence of the rupture of swelling bag on surface with following benchmark
The dregs attachment of cause and with the presence or absence of rough coat (referring to table 1).
(1) the foaming dregs attachment on surface
〇：No
Δ：See a little
×：See a large amount of
(2) epidermis is coarse
〇：It is smooth
Δ：It is a little coarse
×：It is coarse
Further using rubber composition as moulding material, carried out under conditions of 180 DEG C of temperature and 90~360 seconds time
Injection molding, it is continuous to manufacture the harness lantern ring.
In the cycle of measure at this time, judge productivity according to following benchmark.
〇：1.5~3.5 minutes
Δ：3.6~5.0 minutes
×：More than 5.0 minutes
[table 1]
2. the manufacture and evaluation of rubber product
Embodiment 2-1~2-10 and comparative example 2-1~2-4
Rubber composition C1~C10 and C11~C14 are supplied into injection molding, the manufacture lantern ring respectively.Specifically, in advance
Arranged with as shown in Figure 4 formed so that a part for harness 22 is exposed to the chamber formed in mould 32 and 34
Room 38, is formed as the rubber composition of flow regime from being set as that 180 DEG C are molded into by being heated to 80 DEG C by extruder
The raw material entrance hole 36 of type mould 30 supplies (9~12 seconds injection time) and arrives chamber 38, full of chamber 38.After 160 seconds, open
Die injection moulding 30.Operation more than, obtains the integrated article 20 comprising harness portion 22 and collar portion 24.With regard to reality
For applying the collar portion 24 obtained in a 2-1~2-10, relative to chamber 38, the expansion rate for being in terms of volume reference 5~10%.
Using rubber composition C11 comparative example 2-1 Δ t more than 4.5 minutes, therefore proportion be 1.00, the cycle is more than 5
Minute, productivity is insufficient.In comparative example 2-2~2-3 using rubber composition C12 and C13, proportion height, table have been obtained
Face is attached with the collar portion 24 of foaming dregs.In addition, using rubber composition C14 comparative example 2-4 in, although obtained than
Weight is low but the undesirable collar portion 24 of epidermis.On the other hand, the embodiment 2-1~2-10 obtained using rubber composition C1~C10
Collar portion 24 in, do not find such bad situation, aesthetic appearance is good.
Industrial applicability
The rubber composition of the present invention is suitable for generally using and the manufacture of industrial cross-linked rubber article, especially suitable for
Such as the vehicle component of the lantern ring, weather strip, glass run, side filler rod, smooth assembling (flash mount molding) etc.；
The rubber bushing of cableties etc.；The manufacture of sealing material etc..
The explanation of symbol
10：Cableties, 12：Flange part, 14：Line insertion section, 16：Valve portion, 18：Line maintaining part, 20：The one of harness and the lantern ring
Compound, 22：Harness (portion), 24：The lantern ring (portion), 26：Path canister portion, 28：Major diameter canister portion, 30：Die injection moulding, 32：
1st mould, 34：2nd mould, 36：Raw material entrance hole, 38：Chamber.
Claims (11)
1. a kind of rubber composition, it is to carry out the rubber of the thermal expansivity micro-capsule of volumetric expansion containing rubber and by heating
Composition, it is characterised in that
Relative to the rubber of 100 mass parts, the content of the thermal expansivity micro-capsule is 1.5~10.7 mass parts,
With the condition of 0.5 degree of 180 DEG C of temperature, frequency 100cpm and amplitude angle to comprising containing the rubber, the thermal expansion
Property micro-capsule and the uncrosslinked test film of rubber composition of crosslinking agent be heat-treated and it is carried out cross-linking reaction and the heat
In the case of the volumetric expansion of dilatancy micro-capsule, the test film due to heat treatment is expanded and when showing maximum pressure when
Between t1With time t during optimal crosslinking points by JIS K6300-2 defineds2Time difference Δ t (=t2-t1) it is 1.0~4.5
Minute.
2. the rubber composition described in claim 1, wherein, the maximum swelling temperature of the thermal expansivity micro-capsule for 140 DEG C with
On.
3. the rubber composition described in claim 1 or 2, wherein, the particle diameter of the thermal expansivity micro-capsule is 18~50 μm.
4. any one of them rubber composition of claims 1 to 3, wherein, for the thermal expansivity micro-capsule, comprising
The inside of the shell of thermoplastic resin material, contains liquid compound.
5. any one of them rubber composition of Claims 1 to 4, wherein, the rubber includes ethene-alpha-olefin system rubber
Glue.
6. any one of them rubber composition of Claims 1 to 5, it also contains crosslinking agent.
7. any one of them rubber composition of claim 1~6, it is used for injection molding.
8. the rubber composition described in claim 6 or 7, it is to make for 2~5 minutes the deadline for making the cross-linking reaction
Crosslinked rubber composition.
9. a kind of cross-linked rubber article, it is made by the rubber composition described in usage right requirement 6.
10. the cross-linked rubber article described in claim 9, it is the harness lantern ring or rubber bushing.
11. a kind of manufacture method of cross-linked rubber article, it is characterised in that possess the rubber composition described in claim 6
The process for carrying out injection molding.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2015205846 | 2015-10-19 | ||
| JP2015-205846 | 2015-10-19 | ||
| PCT/JP2016/077192 WO2017068893A1 (en) | 2015-10-19 | 2016-09-14 | Rubber composition, and crosslinked rubber product and method for producing same |
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| Publication Number | Publication Date |
|---|---|
| CN107922665A true CN107922665A (en) | 2018-04-17 |
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ID=58557225
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| CN201680048011.4A Pending CN107922665A (en) | 2015-10-19 | 2016-09-14 | Rubber composition and cross-linked rubber article and its manufacture method |
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| Country | Link |
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| JP (1) | JP6814740B2 (en) |
| CN (1) | CN107922665A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020076037A1 (en) * | 2018-10-08 | 2020-04-16 | 이수정 | High-elasticity extruded foam composition |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2019124223A1 (en) * | 2017-12-18 | 2019-06-27 | 三井化学株式会社 | Crosslinked molding and method for manufacturing same |
| KR102010457B1 (en) * | 2018-02-13 | 2019-08-13 | 화인케미칼 주식회사 | Composition for low density molded foam article and method of fabricating molded foam article using the same |
| WO2022091599A1 (en) * | 2020-10-27 | 2022-05-05 | デンカ株式会社 | Rubber foam composition, foam and molded article |
| JP2023167232A (en) * | 2022-05-11 | 2023-11-24 | サンスター技研株式会社 | Foaming curable composition |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035646A1 (en) * | 2003-10-15 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire and pneumatic tire made therefrom |
| JP2007112244A (en) * | 2005-10-19 | 2007-05-10 | Nishikawa Rubber Co Ltd | Automobile weatherstrip and its manufacturing method |
| JP2007186559A (en) * | 2006-01-12 | 2007-07-26 | Kinugawa Rubber Ind Co Ltd | Formed polymer article and weather strip for automobile |
| CN101346218A (en) * | 2005-12-27 | 2009-01-14 | 积水化学工业株式会社 | Molded foam article and method of producing molded foam article |
| CN101412821A (en) * | 2007-10-17 | 2009-04-22 | 横滨橡胶株式会社 | Rubber composition for tire |
| JP2009202353A (en) * | 2008-02-26 | 2009-09-10 | Canon Chemicals Inc | Manufacturing method of rubber roller and rubber roller |
| WO2010050628A2 (en) * | 2009-06-22 | 2010-05-06 | 宇部興産株式会社 | Foamed rubber composition for shoe sole and outersole |
| JP2010275335A (en) * | 2009-05-26 | 2010-12-09 | Kinugawa Rubber Ind Co Ltd | Rubber molded product and process for producing rubber molded product |
| CN102203205A (en) * | 2008-11-07 | 2011-09-28 | 积水化学工业株式会社 | Thermally expandable microcapsule and foam-molded article |
| JP2011256223A (en) * | 2010-06-07 | 2011-12-22 | Toyoda Gosei Co Ltd | Foamed rubber molded article and method for producing the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7820095B2 (en) * | 2006-08-14 | 2010-10-26 | Twist Engine, Inc. | Material with enhanced thermal properties |
-
2016
- 2016-09-14 CN CN201680048011.4A patent/CN107922665A/en active Pending
- 2016-09-14 JP JP2017546454A patent/JP6814740B2/en active Active
- 2016-09-14 WO PCT/JP2016/077192 patent/WO2017068893A1/en active Application Filing
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005035646A1 (en) * | 2003-10-15 | 2005-04-21 | The Yokohama Rubber Co., Ltd. | Rubber composition for tire and pneumatic tire made therefrom |
| JP2007112244A (en) * | 2005-10-19 | 2007-05-10 | Nishikawa Rubber Co Ltd | Automobile weatherstrip and its manufacturing method |
| CN101346218A (en) * | 2005-12-27 | 2009-01-14 | 积水化学工业株式会社 | Molded foam article and method of producing molded foam article |
| JP2007186559A (en) * | 2006-01-12 | 2007-07-26 | Kinugawa Rubber Ind Co Ltd | Formed polymer article and weather strip for automobile |
| CN101412821A (en) * | 2007-10-17 | 2009-04-22 | 横滨橡胶株式会社 | Rubber composition for tire |
| JP2009202353A (en) * | 2008-02-26 | 2009-09-10 | Canon Chemicals Inc | Manufacturing method of rubber roller and rubber roller |
| CN102203205A (en) * | 2008-11-07 | 2011-09-28 | 积水化学工业株式会社 | Thermally expandable microcapsule and foam-molded article |
| JP2010275335A (en) * | 2009-05-26 | 2010-12-09 | Kinugawa Rubber Ind Co Ltd | Rubber molded product and process for producing rubber molded product |
| WO2010050628A2 (en) * | 2009-06-22 | 2010-05-06 | 宇部興産株式会社 | Foamed rubber composition for shoe sole and outersole |
| JP2011256223A (en) * | 2010-06-07 | 2011-12-22 | Toyoda Gosei Co Ltd | Foamed rubber molded article and method for producing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020076037A1 (en) * | 2018-10-08 | 2020-04-16 | 이수정 | High-elasticity extruded foam composition |
| CN112839986A (en) * | 2018-10-08 | 2021-05-25 | 李受柾 | Composition of highly elastic extruded foam |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2017068893A1 (en) | 2018-08-09 |
| JP6814740B2 (en) | 2021-01-20 |
| WO2017068893A1 (en) | 2017-04-27 |
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