CN101421120A - Pneumatic tire - Google Patents
Pneumatic tire Download PDFInfo
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- CN101421120A CN101421120A CNA200580041097XA CN200580041097A CN101421120A CN 101421120 A CN101421120 A CN 101421120A CN A200580041097X A CNA200580041097X A CN A200580041097XA CN 200580041097 A CN200580041097 A CN 200580041097A CN 101421120 A CN101421120 A CN 101421120A
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- rubber
- natural rubber
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Abstract
A pneumatic tire which offers extremely excellent durability through inclusion of a belt portion composed of a rubber composition having excellent reinforcing properties, high hardness, low heat build-up properties, excellent deterioration resistance, and excellent adhesiveness to steel cords, wherein the rubber composition contains a natural rubber prepared by graft polymerizing a natural rubber latex with a polar group-containing monomer, and solidifying and drying the resulting product. A pneumatic tire which offers excellent rolling resistance through inclusion of a ply coating rubber, squeegee rubber, or tie rubber composed of a rubber composition containing a modified natural rubber prepared by graft polymerizing a natural rubber latex with a polar group-containing monomer, and solidifying and drying the resulting product.
Description
Technical field
The present invention relates to air-inflation tyre.
Background technology
The rubber that constitutes airtyred steel wire bracing ply portion is to the influential important rubber of the durability of tire, as its desired characteristic, can list:
(1) reinforcement
(2) hardness
(3) low heat generation
(4) resistance to ag(e)ing
(5) with the adhesive bonding property of steel cord
Deng.Here, the reinforcement that increases (1) is to suppressing effective by the be full of cracks growth from bracing ply end (steel cord end) beginning that interlaminar shearing strain caused between the bracing ply, the hardness that improves (2) is effective to the interlaminar shearing strain that suppresses between the bracing ply, the low heat generation of (3) to suppress tyre surface and bracing ply interface peel off and agingly wait, the raising durability is effective.
At present, the rubber of these bracing ply portions uses natural rubber (NR) always, in order to improve above-mentioned characteristic, has carried out:
(a) increase the combined amount of extending agents such as carbon black.
(b) add curing agent such as resin.
(c) increase the combined amount of crosslinking agents such as sulphur.
(d) combined amount of increase vulcanization accelerator.
Deng, but the characteristic of aforementioned (1)～(5) is all improved be unusual difficulty.
That is, the combined amount by (a) increases carbon black can improve reinforcement, but exist heat generation to reduce simultaneously, the tendency that the heating durability worsens.In addition, hardness is increased, but exist heat generation to reduce, the tendency that the heating durability worsens even (b) add resin.(c) combined amount of increase sulphur, when placing with the state of half finished rubber, sulphur generation bloom (bloom), viscosity reduction etc., operability significantly reduce.In addition, owing to reduce as the resistance to ag(e)ing of tire, even therefore can improve hardness, the situation that also exists durability to reduce.(d) vulcanization accelerator is no problem on operability, low heat generation, resistance to ag(e)ing, but if a large amount of adhesive bonding property that then hinders with steel cord that mixes, adhesion durability reduces as a result.
All there is the problem that rubber composition viscosity uprises, processability reduces in method in addition, (a)～(d).
In recent years, air-inflation tyre is required the low-rolling-resistance of height.
In various robber materialses, natural rubber mainly is used to the carcass plies parts as anti-destructive excellent raw MAT'L.Yet, different with the neoprene that the SB rubber, the poly-butadiene rubber that reduce the wastage by terminal-modified technology are such, the present technology that in natural rubber, does not also reduce the wastage by the improvement rubber constituent, therefore, can't cover glue with cord and significantly reduce rolling resistance.
On the other hand, in the such method of the method for filling doses such as known all the time minimizing carbon black, the degradation of carbon black, although can realize the reduction of loss, anti-destructiveness also reduces simultaneously, can't keep the necessary performance of covering glue as cord, i.e. durability.
Therefore, the natural rubber composition of keeping breakage resistance and can reducing rolling resistance is developed in expectation.
Summary of the invention
First purpose of the present invention is, solve above-mentioned problems of the prior art, by by reinforcement excellence, high hardness, low heat generation, resistance to ag(e)ing excellence, constitute bracing ply portion, thereby provide durability significantly excellent air-inflation tyre with the also excellent rubber composition of the adhesive bonding property of steel cord.
The air-inflation tyre of first form of the present invention is characterized in that, the rubber composition that constitutes bracing ply portion comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
By use with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, the dry modified natural rubber that forms is as rubber constituent, bracing ply covers the reinforcement increase of bracing ply portions such as glue, and suppress heat generation significantly, thereby improvement resistance to ag(e)ing and anti-be full of cracks are expansionary, also improve processability simultaneously, and can not damage with the adhesive bonding property ground of steel cord and constitute bracing ply portion, can provide durability significantly excellent air-inflation tyre thus.
The mechanism of action of this effect is presumed as follows, promptly, by using above-mentioned modified natural rubber, low loss characteristic improves, and the heating that causes when travelling wearing out reduces, therefore can suppress the carrying out that wear out, in addition, by using above-mentioned modified natural rubber, extending agent such as carbon black and rubber is mutual action energetically, the reinforcement raising, the expansionary raising of anti-be full of cracks.
The position that is suitable for the rubber composition comprise modified natural rubber is preferably: the bracing ply that is selected from of bracing ply portion covers rubber more than a kind or 2 kinds in the group that glue is formed between glue (belt coating rubber), bracing ply end glue (beltend rubber) and bracing ply.
Second purpose of the present invention is, by improving the rubber property that cord covers glue (ply coatingrubber), insulation rubber (squeegee rubber) or squeegee (tie gum), thereby provide the air-inflation tyre that does not damage durability and low-rolling-resistance excellence.
The air-inflation tyre of second form of the present invention is characterized in that, cord covers glue and formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
The air-inflation tyre of the 3rd form of the present invention is characterized in that, insulation rubber is formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
The air-inflation tyre of the 4th form of the present invention is characterized in that, squeegee is formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
By use with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, the dry modified natural rubber that forms is as rubber constituent, can fully keep anti-destructiveness and obtain low loss characteristic, rubber composition that rolling resistance is little.Therefore, use this rubber composition in glue, insulation rubber or the squeegee, can realize the air-inflation tyre that low-rolling-resistance excellence and durability are also excellent by covering at airtyred cord.
The specific embodiment
The modified natural rubber that is comprised in the rubber composition is described.
This modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
This Heveatex is common Heveatex, the latex that takes off albumen latex and these combinations are obtained of can list fresh latex, ammonia treatment latex, centrifugalization concentrated latex, handling through inhibiter, enzyme etc.
As the polar functionalities monomer, just be not particularly limited so long as have the monomer of at least one polar group in the molecule.The object lesson of the polar group that is had as this polar functionalities monomer; can list amino, imino group, itrile group, ammonium, imide, amide group, 1,2-hydrazono-, azo group, diazo, hydroxyl, carboxyl, carbonyl, epoxy radicals, oxygen carbonyl, thioether group, disulfide base, sulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle, alkoxysilane group and contain tinbase etc.The monomer that contains these polar groups can be used alone, or two or more kinds may be used in combination.The polar functionalities monomer can only contain a kind of these polar groups, also can contain more than 2 kinds.
Below, list the object lesson of polar functionalities monomer.
As containing amino monomers, have and have the polymerizable monomer that is selected from least 1 amino in primary amino radical, secondary amino group and the uncle's amino in 1 molecule.Wherein, such tertiary-amino-containing monomer such as preferred especially (methyl) acrylic acid dialkylaminoalkyl ester.In addition, in this manual, " (methyl) acryloyl group " is meant " acryloyl group or methacryl ", and " (methyl) acrylate " is meant " acrylate or methacrylate ".
As containing the primary amino radical monomer, for example can list acrylamide, Methacrylamide, 4-vinyl aniline, (methyl) acrylic-amino methyl esters, (methyl) acrylic-amino ethyl ester, (methyl) acrylic-amino propyl ester, (methyl) acrylic-amino butyl ester etc.
As containing the secondary amino group monomer, for example can list,
(1) anilino styrene, beta-phenyl-to anilino styrene, beta-cyano-to anilino styrene, beta-cyano-Beta-methyl-to anilino styrene, β-chloro-is to anilino styrene, β-carboxyl-to anilino styrene, the beta-methoxy-carbonyl-to anilino styrene, β-(2-'-hydroxyethoxy) carbonyl-to anilino styrene, β-formoxyl-to anilino styrene, β-formoxyl-Beta-methyl-to anilino styrene, α-carboxyl-β-carboxyl-beta-phenyl-to such anilino phenylethylenes such as anilino styrene;
(2) anilino phenyl butadiene, 1-anilino phenyl-1,3-butadidenne, 1-anilino phenyl-3-methyl isophthalic acid, 3-butadidenne, 1-anilino phenyl-3-chloro-1,3-butadidenne, 3-anilino phenyl-2-methyl isophthalic acid, 3-butadidenne, 1-anilino phenyl-2-chloro-1,3-butadiene, 2-anilino phenyl-1,3-butadiene, 2-anilino phenyl-3-methyl isophthalic acid, 3-butadidenne, 2-anilino phenyl-anilino phenyl butadiene classes such as 3-chloro-1,3-butadiene;
(3) single (methyl) acrylic amide etc. that replaces of N-such as N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N hydroxymethyl acrylamide, N-(4-anilino phenyl) Methacrylamide.
As the tertiary-amino-containing monomer, can list acrylic acid N, N-disubstituted amido Arrcostab, N, have the vinyl compound of pyridine radicals etc. at N-disubstituted amido alkyl acrylamide.
As aforesaid propylene acid N, N-disubstituted amido Arrcostab, for example can list, (methyl) acrylic acid N, N-dimethylamino methyl esters, (methyl) acrylic acid N, the N-dimethylaminoethyl, (methyl) acrylic acid N, N-dimethylamino propyl ester, (methyl) acrylic acid N, N-dimethylamino butyl ester, (methyl) acrylic acid N, the N-lignocaine ethyl ester, (methyl) acrylic acid N, N-lignocaine propyl ester, (methyl) acrylic acid N, N-lignocaine butyl ester, (methyl) acrylic acid N-methyl-N-ethylamino ethyl ester, (methyl) acrylic acid N, N-dipropyl amino ethyl ester, (methyl) acrylic acid N, N-dibutylamino ethyl ester, (methyl) acrylic acid N, N-dibutylamino propyl ester, (methyl) acrylic acid N, N-dibutylamino butyl ester, (methyl) acrylic acid N, N-two own amino ethyl esters, (methyl) acrylic acid N, N-two hot amino ethyl esters, the ester of acrylic or methacrylic acid such as acryloyl morpholine etc.Preferred especially (methyl) acrylic acid N, N-dimethylaminoethyl, (methyl) acrylic acid N, N-lignocaine ethyl ester, (methyl) acrylic acid N, N-dipropyl amino ethyl ester, (methyl) acrylic acid N, N-two hot amino ethyl esters, (methyl) acrylic acid N-methyl-N-ethylamino ethyl ester etc.
As N, N-disubstituted amido alkyl acrylamide, for example can enumerate, N, N-dimethylamino methyl (methyl) acrylamide, N, N-dimethylaminoethyl (methyl) acrylamide, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-dimethylamino butyl (methyl) acrylamide, N, N-diethyllaminoethyl (methyl) acrylamide, N, N-lignocaine propyl group (methyl) acrylamide, N, N-lignocaine butyl (methyl) acrylamide, N-methyl-N-ethylamino ethyl (methyl) acrylamide, N, N-dipropyl amino-ethyl (methyl) acrylamide, N, N-dibutylamino ethyl (methyl) acrylamide, N, N-dibutylamino propyl group (methyl) acrylamide, N, N-dibutylamino butyl (methyl) acrylamide, N, N-two own amino-ethyl (methyl) acrylamides, N, N-two own aminopropyl (methyl) acrylamides, N, acrylamide compound such as N-two hot aminopropyl (methyl) acrylamides or methacryl amines etc.In the middle of these, preferred especially N, N-dimethylamino-propyl (methyl) acrylamide, N, N-lignocaine propyl group (methyl) acrylamide, N, N-two hot aminopropyl (methyl) acrylamides etc.
As vinyl compound, for example can list 2-vinylpyridine, 3-vinylpyridine, 4-vinylpridine, 5-methyl-2-vinylpyridine, 5-ethyl-2-vinylpyridine etc. with pyridine radicals.Preferred especially 2-vinylpyridine, 4-vinylpridine etc. in the middle of these.
As the nitrogen heterocyclic ring of monomer, for example can list pyrroles, histidine, imidazoles, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indoles, quinoline, purine, azophenlyene, pteridine, melamine etc. with nitrogen heterocycle.Nitrogen heterocyclic ring can also comprise other heteroatoms in ring.
As the nitrile group-containing monomer, for example can list (methyl) acrylonitrile, vinylidene cyanide etc.
As the hydroxyl monomer, can list the polymerizable monomer that has at least 1 primary hydroxyl, secondary hydroxyl and tert-hydroxyl in 1 molecule.As this monomer, for example hydroxyl unsaturated carboxylic acid class monomer, hydroxyl vinyl ethers monomer, hydroxyl vinyl ketones monomer etc. are arranged.Object lesson as such hydroxyl monomer has: (methyl) acrylic acid hydroxy alkyl ester classes such as (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate, (methyl) acrylic acid 3-hydroxypropyl acrylate, (methyl) acrylic acid 2-hydroxy butyl ester, (methyl) acrylic acid 3-hydroxy butyl ester, (methyl) acrylic acid 4-hydroxy butyl ester; List (methyl) esters of acrylic acid of such PAG such as carbowax, polypropylene glycol (aklylene glycol unit numerical example as be 2～23); N-methylol (methyl) acrylamide, N-(2-ethylol) (methyl) acrylamide, N, hydroxyl unsaturated acyl amines such as two (2-methylol) (methyl) acrylamides of N-; O-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene, adjacent hydroxyl-AMS, hydroxyl-AMS, to hydroxyl-AMS, to hydroxyl vinyl aromatic compounds classes such as vinyl benzene methyl alcohol; (methyl) esters of acrylic acid.In the middle of these, preferred hydroxyl unsaturated carboxylic acid class monomer, (methyl) acrylic acid hydroxy alkyl ester class, hydroxyl vinyl aromatic compounds, preferred especially hydroxyl unsaturated carboxylic acid class monomer.As hydroxyl unsaturated carboxylic acid class monomer, the derivants such as ester, acid amides, acid anhydrides of acrylic acid, methyl acrylic acid, itaconic acid, fumaric acid, maleic acid etc. are for example arranged, the ester compounds of preferred especially acrylic acid, methyl acrylic acid etc.
As containing carboxylic monomer, can list unsaturated carboxylic acid classes such as (methyl) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, cinnamic acid; Perhaps the monoesters of hydroxyl unsaturated compounds such as non-polymerization polybasic carboxylic acids such as phthalic acid, succinate, adipic acid and (methyl) allyl alcohol, (methyl) acrylic acid 2-hydroxyl ethyl ester is such contains free carboxy ester class and salt thereof etc.Preferred especially unsaturated carboxylic acid class in the middle of these.
As containing the epoxy radicals monomer, can list (methyl) allyl glycidyl ether, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-oxygen cyclohexyl etc.
As the monomer that contains alkoxysilane group, for example can list, (methyl) acryloyl-oxy MTMS, (methyl) acryloyl-oxy methyl dimethoxy silane, (methyl) acryloyl-oxy methyl dimethoxy methoxylsilane, (methyl) acryloyl-oxy MTES, (methyl) acryloyl-oxy methyl diethoxy silane, (methyl) acryloyl-oxy methyl dimethoxy base oxethyl silane, (methyl) acryloyl-oxy methyl tripropoxy silane, (methyl) acryloyl-oxy methyl dipropoxy silane, (methyl) acryloyl-oxy methyl dimethoxy base propoxyl group silane, γ-(methyl) acryloyl-oxy propyl trimethoxy silicane, γ-(methyl) acryloyl-oxy propyl group methyl dimethoxysilane, γ-(methyl) acryloyl-oxy propyl-dimethyl methoxy silane, γ-(methyl) acryloyl-oxy propyl-triethoxysilicane, γ-(methyl) acryloyl-oxy propyl group methyldiethoxysilane, γ-(methyl) acryloyl-oxy propyl-dimethyl Ethoxysilane, γ-(methyl) acryloyl-oxy propyl group tripropoxy silane, γ-(methyl) acryloyl-oxy propyl group methyl dipropoxy silane, γ-(methyl) acryloyl-oxy propyl-dimethyl propoxyl group silane, γ-(methyl) acryloyl-oxy propyl group methyldiphenyl TMOS, γ-(methyl) acryloyl-oxy propyl-dimethyl phenoxy group silane, γ-(methyl) acryloyl-oxy propyl group methyl benzyloxy silane, γ-(methyl) acryloyl-oxy propyl-dimethyl benzyloxy silane, the trimethoxy vinyl silanes, the triethoxy vinyl silanes, 6-trimethoxy silane base-1, the 2-hexene, to trimethoxy silane base styrene etc.
As the stanniferous monomer, for example can list allyl tri-n-butyl tin, allyl tin trimethyl, allyl triphenyltin, allyl three n-octyl tin, (methyl) acryloxy normal-butyl tin, (methyl) acryloxy tin trimethyl, (methyl) acryloxy triphenyltin, (methyl) acryloxy n-octyl tin, vinyl tri-n-butyl tin, vinyl tin trimethyl, vinyl triphenyltin, vinyl three n-octyl tin etc.
Modified natural rubber can add the initiating agent that graft polymerization is used again by for example add the polar functionalities monomer in Heveatex, carries out emulsion polymerization then, then the poly-mer that is generated is solidified, dry and obtain.
Initiating agent as graft polymerization is used is not particularly limited, and can use various initiating agents, and for example the initiating agent that can use emulsion polymerization to use also is not particularly limited its adding method.Example as common employed initiating agent, can list benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, TBHP, di-tert-butyl peroxide, 2,2-azobis isobutyronitrile, 2, two (2-diaminopropanes) hydrochlorides, 2 of 2-azo, two (2-diaminopropanes) dihydrochlorides, 2 of 2-azo, 2-azo two (2, the 4-methyl pentane nitrile), potassium persulfates, sodium peroxydisulfate, ammonium persulfate etc.In addition, in order to reduce polymerization temperature, preferably use the polymerization initiator of redox system.As with the deoxidation compound of the peroxide combination that is used for this redox system polymerization initiator, for example can list tetren, thio-alcohol, acid sodium sulphite, reducing metal ion, ascorbic acid etc.The combination of special preferred tertiary butylhydroperoxide and tetren is as the redox system polymerization initiator.
Graft polymerization can be the common emulsion polymerization of adding aforesaid polar functionalities monomer and polymerization while stirring under the temperature of regulation in Heveatex.Here, can be in the polar functionalities monomer, to add entry and emulsifying agent in advance, adequately emulsified material is added in the Heveatex; Also can be that the polar functionalities monomer is directly added in the Heveatex, before adding monomer or after adding monomer, add emulsifying agent as required.
As emulsifying agent, be not particularly limited, can list the nonionic class inhibiter as polyoxyethylene laurel ether etc.
Bring into play effect of the present invention effectively and processability when not being reduced in mixed carbon black in the rubber composition, silicon dioxide if consider, importantly the molecule to natural rubber imports a spot of polar group equably, therefore, with respect to 100 moles of polar functionalities monomers, the addition of polymerization initiator is preferably 1～100 mole of %, more preferably 10～100 moles of %.
Modified natural rubber can followingly obtain, promptly, in reaction vessel, add above-mentioned each composition, graft polymerization was carried out in reaction in 10 minutes～7 hours under 30～80 ℃, thereby obtain modified natural rubber latex, after this modified natural rubber latex solidified, washs, use dryers such as vacuum desiccator, air dryer, drum dryer to carry out drying and obtain.
The grafting amount of polar functionalities monomer with respect to the rubber constituent of Heveatex be preferably 0.01～5.0 weight %, more preferably 0.1～3.0 weight %, be preferably 0.2～1.0 weight % especially.During the grafting quantity not sufficient 0.01 weight % of polar functionalities monomer, can't fully obtain the effect of the present invention of using this modified natural rubber to bring, if surpass 5.0 weight %, then may damage the characteristic of the intrinsic excellence of visoelasticity, S-S characteristic natural rubbers such as (deformability load curves of tensile machine), and might reduce processability.
Rubber composition contains such modified natural rubber as rubber constituent, preferably contain 10 weight % above, more preferably 40 weight % above, especially be preferably 60 weight % above, more preferably 60～100 weight %, especially be preferably 80～100 weight %.Here, modified natural rubber contain the above-mentioned lower limit of quantity not sufficient, can't fully obtain the effect of the present invention of using this modified natural rubber to bring.
As other rubber constituent of using with modified natural rubber, can list common natural rubber and dienes neoprene.As the dienes neoprene, can list for example SB (SBR), poly-butadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer etc.These other rubber constituents can be used a kind separately, also can will be used in combination more than 2 kinds.
Rubber composition can contain the above-mentioned modified natural rubber of 30～60 weight % and dienes neoprene such as 10～30 weight %SBR, BR as rubber constituent, can realize that thus good low heat generation and Gao Nai are destructive and deposits.
Rubber composition preferably contains carbon black as extending agent.With respect to 100 parts by weight of rubber compositions in the rubber composition, the combined amount of carbon black is preferably 30～120 weight portions.During these combined amount less than 30 weight portions, can't fully the obtain mixed carbon black reinforcement that is brought, the improved effect of other rerum natura, when combined amount surpasses 120 weight portions, reductions such as processability.
Carbon black can use all commercially available carbon blacks, wherein preferably uses the carbon black of SAF, ISAF, HAF, FEF, GPF grade, and the preferred especially DBP uptake of carbon black is 110 * 10
-5m
3More than/the kg, the nitrogen adsorption specific surface area is 140 * 10
3m
2More than/the kg.
When containing carbon black in the rubber composition, replace its part, for example contain 2～50 weight portions, especially 10～30 weight portion silicon dioxide, can improve heat generation thus with respect to 100 parts by weight of rubber compositions with silicon dioxide.Here, silicon dioxide can use commercially available all silicon dioxide, wherein preferably uses wet silicon dioxide, dry type silicon dioxide, cataloid.The BET specific surface area of silicon dioxide is preferably 150m
2/ g is above, 170m more preferably
2/ g is above, be preferably 190m especially
2More than/the g.Such silicon dioxide can use commercially available products such as " NIPSEAL AQ " that TOSOH SILICA CORPORATION produces, " NIPSEAL KQ ".
Carbon black, silicon dioxide can use a kind separately, also can will be used in combination more than 2 kinds.
In addition, in rubber composition during mixed silica, the aspect that can obtain excellent mixed effect from silicon dioxide and modified natural rubber firm combining and by the mutual action of silicon dioxide and modified natural rubber considers, modified natural rubber has preferably used graft polymerization and contained the modified natural rubber of alkoxysilane group monomer.
As required, rubber composition can suitably be blended in the normally used compounding ingredient of rubber industry according to purpose, for example, and other reinforcement extending agent, vulcanizator, vulcanization accelerator, aging inhibitor, soften flux etc.
In the air-inflation tyre of the present invention's first form, bracing ply portion, to be preferably selected from that bracing ply covers in the group that glue is formed between glue, bracing ply end glue and bracing ply be to be made of the rubber composition that comprises above-mentioned modified natural rubber more than a kind or 2 kinds.The air-inflation tyre of first form can be made the composition same with existing air-inflation tyre except bracing ply portion is made of the above-mentioned rubber composition that comprises above-mentioned natural rubber, its manufacture method also is not particularly limited, can be according to the conventional approach manufacturing.
In the air-inflation tyre of second to the 4th form of the present invention, it is to be made of the rubber composition that comprises above-mentioned modified natural rubber that cord covers glue, insulation rubber or squeegee, this air-inflation tyre can be that cord covers and has only 1 to be made of above-mentioned rubber composition in glue, insulation rubber or the squeegee, also can be two in these or is made of above-mentioned rubber composition all.This air-inflation tyre covers glue, insulation rubber or squeegee be made of the rubber composition that comprises above-mentioned modified natural rubber except cord, can make the composition same with existing air-inflation tyre, and its manufacture method also is not particularly limited, can be according to the conventional approach manufacturing.
Air-inflation tyre of the present invention can be applicable to effectively from city motor bus, truck, the such heavy duty of aircraft uses car, motor sport contests such as (MS) with the various air-inflation tyres such as car air-inflation tyre with air-inflation tyre to taking.
Embodiment
List Production Example, embodiment and comparative example below first form of the present invention is carried out more specific description, first form only otherwise exceed the qualification that its spirit just is not subjected to following embodiment.
Production Example 1: the manufacture method of modified natural rubber
(1) the modified-reaction operation of Heveatex
Use latex disconnector (SAITO SEPARATOR LIMITED production) fresh latex to be carried out centrifugalization, obtain dry rubber concentrations and be 60% concentrated latex with revolution 7500rpm.This concentrated latex of 1000g put into possess mixer, in the stainless steel reaction vessel of temperature adjustment chuck, in the 3.0g4-vinylpyridine, add 10ml water and 90mg emulsifying agent (EMUL GEN 1108 in advance, Kao Corp's production) carry out emulsification, the material of gained is added in the above-mentioned reaction vessel with 990ml water, and the limit is carried out the nitrogen replacement limit to it and was stirred 30 minutes.Then, add 1.2g TBHP and 1.2g tetren, reacted 30 minutes down, obtain modified natural rubber latex thus at 40 ℃ as polymerization initiator.
(2) solidify, drying process
Then, add formic acid pH is adjusted into 4.7, thereby modified natural rubber latex is solidified.The solid matter that obtains is like this handled 5 times with clappers, broken into pieces, utilize air drier to descend dry 210 minutes, obtain modified natural rubber A at 110 ℃ by shredder.Can confirm from the weight of the modified natural rubber A that obtains like this: the conversion ratio as the 4-vinylpridine of polar functionalities monomer is 100%.In addition, with this modified natural rubber of petroleum ether extraction, the component solvent with the 2:1 of acetone and methyl alcohol extracts again, thereby carries out the separation of homopolymer, the result does not detect homopolymer from the analysis of extract, has confirmed that the monomer 100% that is added is directed in the natural rubber molecule.
Embodiment 1～3, comparative example 1～5
The rubber composition of prescription carries out following evaluation shown in the his-and-hers watches 1, and the result is shown in the table 1.
In addition, employed each material is as follows in the table 1.
[material of use]
Natural rubber: RSS # 4
Modified natural rubber: 4-vinylpridine 0.5% modified natural rubber of making in the Production Example 1
Silicon dioxide: " the NIPSEAL AQ " that TOSOH SILICA CORPORATION produces
Carbon black: N326 Asahi Carbon Co., " rising sun # 70L " that Ltd. produces
Cobalt salt: " the DICNATE NBC-II " that big Japanese ink chemical frbre industry (strain) is produced
Vulcanization accelerator: " NOCCELER-DZ " (N, N-dicyclohexyl-2-[4-morpholinodithio sulfenamide) that the emerging chemical frbre industry of imperial palace (strain) is produced
Aging inhibitor: " the NOCRAC NS-6 " that the emerging chemical frbre industry of imperial palace (strain) is produced
[evaluation]
(1) store elastic modulus E ' and coefficient of losses tan δ
To under conditions of vulcanization (160 ℃ * 14 minutes), having carried out the rubber composition of sulfuration, use spectrometer (Measurement of Dynamic Viscoelasticity experimental engine), in initial load 160g, frequency 52Hz, strain 1%, measure under 25 ℃ of the temperature and measure, with the situation of comparative example 1 as 100, with exponential representation.
E ' is big more, and the expression modulus of elasticity is high more and good; The low more expression of tan δ is low heat generation.
(2) the breaking extension conservation rate after aging
To under conditions of vulcanization (160 ℃ * 14 minutes), having carried out the rubber composition of sulfuration, based on JIS K6301-1995 (No. 3 test piece), measures the breaking extension of placing aging ageing test front and back in 100 ℃ * 24 hours, air, calculate with following formula.
Conservation rate=100 * (aging back breaking extension)/(breaking extension before aging)
This numerical value is big more, and resistance to ag(e)ing is high more and good.
(3) bloom of placement after 3 days
To under conditions of vulcanization (160 ℃ * 14 minutes), having carried out the rubber composition of sulfuration, after 25 ℃ are placed 3 days down, the visual observation rubber surface for ignoring be judged as " zero " of degree, produces be judged as " * " of white portion with the whiting that bloom produced of sulphur.
(4) adhesive bonding property
Brass coating steel cord (1 * 5 structure, filament diameter: 0.225mm) arrange will have been implemented with the spaced and parallel of 12.5mm, make sample with rubber composition from this steel cord of coating on both sides, the sample that this sample of sulphurization under conditions of vulcanization (160 ℃ * 10 minutes) is obtained, extract steel cord out based on ASTM-D-2229, in the steel cord surface of being extracted out, the visual ratio of obtaining the face area that is covered by rubber.
This numerical value is big more, and the expression binding power is big more and good.
(5) anti-be full of cracks is expansionary
The rubber composition stamping-out that will carry out sulfuration under conditions of vulcanization (160 ℃ * 14 minutes) becomes dumbbell shaped, to have the sample of 5mm be full of cracks in advance at central part, under 80 ℃, chuck spacing 20mm, certain stress, apply the stroke of 7Hz with fatigue tester, with the situation of comparative example 1 as 100, with exponential representation up to the number of times of fracture fully.
This value is big more, and the expression life-span is long more, and anti-be full of cracks is expansionary excellent more.
Table 1
As shown in Table 1, the rubber composition that comprises modified natural rubber of the present invention is low loss characteristic, low heat generation, resistance to ag(e)ing, with adhesive bonding property, the expansionary excellence of anti-be full of cracks of steel cord, therefore, by such rubber composition being used for the air-inflation tyre of the present invention of bracing ply portion, can provide the air-inflation tyre of excellent in te pins of durability.
List Production Example, embodiment and comparative example below second to the 4th form of the present invention is carried out more specific description, second to the 4th form only otherwise exceed the qualification that its spirit just is not subjected to following embodiment.
Production Example 2: the manufacture method of modified natural rubber A
(1) the modified-reaction operation of Heveatex
Use latex disconnector (SAITO SEPARATOR LIMITED production) fresh latex to be carried out centrifugalization, obtain dry rubber concentrations and be 60% concentrated latex with revolution 7500rpm.This concentrated latex of 1000g put into possess mixer, in the stainless steel reaction vessel of temperature adjustment chuck, (EMULGEN 1108 to add 10ml water and 90mg emulsifying agent in advance in the 3.0g2-vinylpyridine, Kao Corp's production) carry out emulsification, the material of gained is added in the above-mentioned reaction vessel with 990ml water, and the limit is carried out the nitrogen replacement limit to it and was stirred 30 minutes.Then, add 1.2g TBHP and 1.2g tetren, reacted 30 minutes down, obtain modified natural rubber latex thus at 40 ℃ as polymerization initiator.
(2) solidify, drying process
Then, add formic acid pH is adjusted into 4.7, thereby modified natural rubber latex is solidified.The solid matter that obtains is like this handled 5 times with clappers, broken into pieces, utilize air drier to descend dry 210 minutes, obtain modified natural rubber A at 110 ℃ by shredder.Can confirm from the weight of the modified natural rubber A that obtains like this: the conversion ratio as the 2-vinylpyridine of polar functionalities monomer is 100%.In addition, with this modified natural rubber of petroleum ether extraction, use 2: 1 component solvent of acetone and methyl alcohol to extract again, thereby carry out the separation of homopolymer, the result does not detect homopolymer from the analysis of extract, has confirmed that the monomer 100% that is added is directed in the natural rubber molecule.Therefore, the modified natural rubber of manufacturing is 2-vinylpyridine 0.5% modified natural rubber.
Production Example 3: the manufacture method of modified natural rubber B
In Production Example 2, except using gamma-methyl allyl acyloxypropyl trimethoxysilane replacement 2-vinylpyridine, carry out same operation, obtain gamma-methyl allyl acyloxypropyl trimethoxysilane 5% modified natural rubber.
Embodiment 4～6, comparative example 6～9
The rubber composition of prescription carries out following evaluation shown in the his-and-hers watches 2, and the result is shown in the table 2.
In addition, employed each material is as follows in the table 2.
[material of use]
Natural rubber: RSS # 4
Modified natural rubber A: 2-vinylpyridine 0.5% modified natural rubber of making in the Production Example 2
Modified natural rubber B: gamma-methyl allyl acyloxypropyl trimethoxysilane 5% modified natural rubber of making in the Production Example 3
SBR:# 1500 (JSR company produces " JSR 1500Z ")
Carbon black: N330 Asahi Carbon Co., " rising sun # 70-NP " that Ltd. produces
Silicon dioxide: " the NIPSEAL AQ " that TOSOH SILICA CORPORATION produces
Bobbin oil: " the Diana Process Oil NS-28 " that the emerging product of bright dipping (strain) is produced
Stearic acid: MIYOSHI OIL﹠amp; FAT CO., the MXST-L that LTD produces "
Vulcanization accelerator: " Sanceler NS-G " (N (tert-butyl group)-2-[4-morpholinodithio sulfenamide) that three new chemical frbre industrys (strain) are produced
[evaluation]
(1) ML
1+4(not vulcanizing viscosity)
Evaluation as the processability of rubber composition, " MOONYVISCOMETERSMV201 " that uses SHIMADZU company to produce, carry out mixing half finished rubber sample 130 ℃ of following preheatings 1 minute with adding sulfuration class compounding ingredient, start the rotation of rotor then, measure value after 4 minutes as ML
1+4This value is big more, and it is high more that viscosity is not vulcanized in expression, and processability is that capacity rating is bad.
(2) disruption characteristic (anti-destructiveness)
To with the 160 ℃ * sample that vulcanized in 20 minutes, obtain 23 ℃ based on JIS K6251-1993 and survey timer-operated pulling strengrths down.This value is big more, and anti-destructiveness is high more.
(3) anti-be full of cracks is expansionary
The rubber composition stamping-out that will vulcanize under conditions of vulcanization (160 ℃ * 20 minutes) becomes dumbbell shaped, to have the sample of 5mm be full of cracks in advance at central part, under 80 ℃, chuck spacing 20mm, certain stress, apply the stroke of 7Hz with fatigue tester, with the situation of comparative example 7 as 100, with exponential representation up to the number of times of fracture fully.This value is big more, and the expression life-span is long more, and anti-be full of cracks is expansionary excellent more.
(4) coefficient of losses tan δ (dynamic viscoelastic)
To the rubber composition that under conditions of vulcanization (160 ℃ * 14 minutes), vulcanizes, the spectrometer (Measurement of Dynamic Viscoelasticity experimental engine) that uses the smart machine of Japan to produce, in initial load 160g, frequency 50Hz, strain 1.0%, measure under 23 ℃ of the temperature and measure, with the situation of comparative example 7 as 100, with exponential representation.Tan δ is big more, and then expression is low-loss.
(5) rolling resistance
Rubber composition is used for cord covers glue, measure the rolling resistance of tire (size 185/70R14) with rotary drum, with the situation of comparative example 7 as 100, with exponential representation.This value is big more, and rolling resistance is more little, the low-rolling-resistance excellence.
Table 2
Following as shown in Table 2 result.
Used in the comparative example 6～9 of existing natural rubber, when increasing the natural rubber amount, the loss of rubber composition reduces, but little to the contribution of tire drag.On the other hand, if increase natural rubber amount, ML
1+4Increase, capacity rating reduces.
In the comparative example 8 that reduces amounts of carbon black in order to obtain low-loss, disruption characteristic, the expansionary all reductions simultaneously of anti-be full of cracks can't have low-rolling-resistance and durability simultaneously concurrently.
A part of carbon black is being replaced in the comparative example 9 of silicon dioxide, though loss reduces, anti-be full of cracks is expansionary significantly to be reduced, and in addition, the increase of viscosity causes capacity rating also to worsen.
In the embodiment 4,5 that has used modified natural rubber, the loss of rubber composition is compared with comparative example 7 and is reduced by 35%, result, the rolling resistance reduction by 3% of tire.In addition, also can keep durability.
A part of carbon black is being replaced among the embodiment 6 of silicon dioxide, and the combination of natural rubber and silicon dioxide indurates by the alkoxy silane of grafting, the result, and durability is compared with comparative example 9 significantly and is improved.
By these results as can be known, the airtyred durability of the present invention, low-rolling-resistance excellence.
The present invention requires to enjoy respectively at the Japanese patent application 2004-346506 of application on November 30th, 2004 and the preceence of Japanese patent application 2004-346507, and quotes its full content.
Claims (12)
1. air-inflation tyre, wherein, bracing ply portion, cord cover glue, insulation rubber and squeegee at least 1 and are formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
2. air-inflation tyre according to claim 1 is characterized in that, at least 1 rubber that bracing ply covers in the group that glue is formed between glue, bracing ply end glue and bracing ply that is selected from of bracing ply portion is formed by described rubber composition.
3. air-inflation tyre according to claim 1 is characterized in that, cord covers glue and formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
4. air-inflation tyre according to claim 1 is characterized in that insulation rubber is formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
5. air-inflation tyre according to claim 1 is characterized in that squeegee is formed by the rubber composition that comprises modified natural rubber, this modified natural rubber by with polar functionalities monomer-grafted be aggregated on the Heveatex and solidify, dry formation.
6. air-inflation tyre according to claim 1 is characterized in that, contains the above described modified natural rubber of 10 weight % of whole rubber constituents in the described rubber composition.
7. air-inflation tyre according to claim 1 is characterized in that, contains the described modified natural rubber of 60～100 weight % of whole rubber constituents in the described rubber composition.
8. air-inflation tyre according to claim 1; it is characterized in that; described polar group is for being selected from amino, imino group, itrile group, ammonium, imide, amide group, 1,2-hydrazono-, azo group, diazo, hydroxyl, carboxyl, carbonyl, epoxy radicals, oxygen carbonyl, thioether group, disulfide base, sulfonyl, sulfinyl, thiocarbonyl, nitrogen heterocycle, oxygen-containing heterocycle, alkoxysilane group and contain in the tinbase more than a kind or 2 kinds.
9. air-inflation tyre according to claim 1 is characterized in that, with respect to the rubber constituent of Heveatex, the grafting amount of described polar functionalities monomer is 0.01～5.0 weight %.
10. air-inflation tyre according to claim 1 is characterized in that described rubber composition comprises carbon black.
11. air-inflation tyre according to claim 10 is characterized in that, described rubber composition comprises silicon dioxide.
12. air-inflation tyre according to claim 1 is characterized in that, this rubber composition also comprises natural rubber and the elastomeric at least one side of dienes.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004346507A JP2006152157A (en) | 2004-11-30 | 2004-11-30 | Pneumatic tire |
| JP346506/2004 | 2004-11-30 | ||
| JP346507/2004 | 2004-11-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101421120A true CN101421120A (en) | 2009-04-29 |
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ID=36630827
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA200580041097XA Pending CN101421120A (en) | 2004-11-30 | 2005-11-18 | Pneumatic tire |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2006152157A (en) |
| CN (1) | CN101421120A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086840A (en) * | 2014-07-02 | 2014-10-08 | 安徽宁国尚鼎橡塑制品有限公司 | Anti-aging rubber material used for automobile |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5069517B2 (en) * | 2007-08-10 | 2012-11-07 | 住友ゴム工業株式会社 | Belt-like ply and pneumatic tire using the same |
| JP2011225678A (en) * | 2010-04-16 | 2011-11-10 | Bridgestone Corp | Rubber composition, belt coating rubber, and pneumatic tire |
| DE112014001128T5 (en) | 2013-03-07 | 2015-12-10 | Toyo Tire & Rubber Co., Ltd. | Process for the preparation of a modified polymer and rubber composition |
-
2004
- 2004-11-30 JP JP2004346507A patent/JP2006152157A/en active Pending
-
2005
- 2005-11-18 CN CNA200580041097XA patent/CN101421120A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086840A (en) * | 2014-07-02 | 2014-10-08 | 安徽宁国尚鼎橡塑制品有限公司 | Anti-aging rubber material used for automobile |
| CN104086840B (en) * | 2014-07-02 | 2016-04-27 | 合肥市再德高分子材料有限公司 | A kind of automobile anti-aging rubber material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2006152157A (en) | 2006-06-15 |
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Open date: 20090429 |