CN100480316C - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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- CN100480316C CN100480316C CNB200580013190XA CN200580013190A CN100480316C CN 100480316 C CN100480316 C CN 100480316C CN B200580013190X A CNB200580013190X A CN B200580013190XA CN 200580013190 A CN200580013190 A CN 200580013190A CN 100480316 C CN100480316 C CN 100480316C
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Abstract
Disclosed is a rubber composition wherein 1-10 parts by mass of sulfur and 0.1-10 parts by mass of a compound represented by the general formula (1) below or a composition mainly containing such a compound are compounded per 100 parts by mass of a rubber component. Also disclosed is a pneumatic tire wherein at least one of a carcass (4) and a belt (6) includes a layer which is composed of a steel cord covered with a coating rubber, which pneumatic tire is characterized in that the above-described rubber composition is used as the coating rubber covering the steel cord in at least one of the carcass (4) and the belt (6). (1) (In the formula, R represents a divalent aliphatic group having 1-16 carbon atoms or a divalent aromatic group.
Description
Technical field
The present invention relates to a kind of rubber combination and use the pneumatic tyre of this rubber combination, this rubber combination has excellent and the adhesion durability metal reinforcement materials such as steel wire cord that are used for rubber items such as pneumatic tyre or industrial belt, more specifically, the present invention relates to a kind of rubber combination, this rubber combination is as the coating rubber of metal reinforcement material, processibility when rubber cooperates is good, do not mixed, the control of preservation condition, change in time little, good to the initial stage cementability and the moisture-proof thermal bonding of metal reinforcement material; Also relate to a kind of pneumatic tyre simultaneously, this pneumatic tyre one deck casingply (carcass ply) at least and/or at least one deck belt (belt layer) be that the cord body portion (carcass) of steel-cord ply and at least one side in the belt portion (belt) use above-mentioned rubber combination, suppress its damp and hot deterioration, thereby improve its weather resistance.
Background technology
Since latter half nineteen forties, company of Michelin developed radial wire cord tire, at least one side in cord body portion and the belt portion uses steel wire cord to strengthen the airtyred market share as the steel wire cord of its reinforcement material to be increased smoothly.Particularly in recent years, along with the transformation to bias belted tyre, radial, this steel wire cord is strengthened the airtyred market share to be increased significantly, and the lorry tire share also increases rapidly.In addition, except that steel wire cord is strengthened pneumatic tyre, in the rubber item of special requirement intensity such as travelling belt, flexible pipe, to strengthen rubber, improve intensity, weather resistance is a purpose, has used the matrix material made from metal reinforcement material such as rubber combination coated steel silk cord.
For making the higher stiffening effect of above-mentioned rubber-metal matrix material performance obtain reliability, stable bonding about conditions such as not mixed between the rubber-metal reinforcement material, cooperation, storage is necessary.For obtaining this complex body, extensively adopt so-called directly sulfuration bonding, that is, will be electroplate with zinc, brass, brass (very
) the metal reinforcement materials such as steel wire cord that wait are embedded among the rubber combination that is combined with sulphur, during baking, in the vulcanization of rubber, make it bonding, up to the present for improve this directly cementability, particularly the moisture-proof thermal bonding between the rubber-metal reinforcement material of sulfuration in bonding carried out various discussions.
For example, there have report to disclose to be a kind of for improving the rubber combination (spy opens the 2001-234140 communique) that resorcinol-formaldehyde resin (hereinafter to be referred as " RF resin ") that the moisture-proof thermal bonding cooperates Resorcinol or Resorcinol and formalin condensation to obtain is made.By cooperating the RF resin, the moisture-proof thermal bonding of steel wire cord and rubber significantly improves really.
Yet,,, may damage the outward appearance of rubber item so the shortcoming and the intermiscibility of rubber because of the condition of mixing, cooperation, storage etc. causes Resorcinol or RF resin to be separated out, so-called frosting take place promptly because the polarity of Resorcinol or RF resin is very high.In addition, because of the generation of frosting, if from cooperating this rubber combination to preserve the problem that will cause cementability to descend for a long time to the bonding warp of sulfuration, therefore it is bonding the rubber combination that is combined with Resorcinol or RF resin promptly to be vulcanized, and reduces the productivity of rubber item probably.
In addition, disclose a kind of adhesives, this adhesives is that 3000～45000 the mixed polyester that contains the Resorcinol skeleton constitutes (spy opens flat 7-118621 communique) by weight-average molecular weight.Yet the mixed polyester that molecular weight is big is compared with the RF resin, though make moderate progress with the intermiscibility of rubber, but still can not meet the demands fully.And, if the high-molecular weight mixed polyester is cooperated with rubber, then there is the problem that viscosity increases, processibility reduces of compound rubber, the moisture-proof thermal bonding is also insufficient.
Summary of the invention
Therefore, the object of the present invention is to provide a kind of rubber combination, this rubber combination can solve above-mentioned prior art problems, in the time of processibility when maintenance cooperates with rubber constituent and high moisture-proof thermal bonding, the frosting that occurs when suppressing to cooperate Resorcinol or RF resin shows to change little and stable cementability in time.
In addition, another object of the present invention is to provide a kind of pneumatic tyre, this pneumatic tyre uses the coating rubber of following rubber combination as its steel-cord ply by at least one side in cord body portion and belt portion, excellent in workability when making preparation, cementability between weather resistance height and steel wire cord and the coating rubber is stable simultaneously, wherein said rubber combination has and the equal moisture-proof thermal bonding of the rubber combination that cooperates Resorcinol or RF resin to obtain, and specific viscosity is low mutually with this rubber combination, the frosting that occurs in the time of can suppressing to cooperate Resorcinol or RF resin shows to change little and stable cementability in time.
The inventor etc. concentrate on studies for achieving the above object, found that, amount cooperates the compound of ad hoc structure or is the rubber combination of the composition gained of main component with this compound in accordance with regulations in rubber constituent, keep and moisture-proof thermal bonding and processibility that the rubber combination that cooperates Resorcinol or RF resin to obtain is equal in, the problem that can suppress this rubber combination existence is the generation of frosting, and have and be not subjected to cooperate, the stable cementability of the conditionality of storage etc., and then, by using the coating rubber of this rubber combination as at least one side's steel-cord ply in cord body portion and the belt portion, compare with the situation of the rubber combination that uses cooperation Resorcinol or RF resin to obtain, improved the processibility when tire prepares, improved the bonding stability between steel wire cord and the coating rubber simultaneously, therefore the tire for preparing has high-durability, thereby has finished the present invention.
That is, being characterized as of rubber combination of the present invention with respect to 100 mass parts rubber constituents (A), cooperates the compound (C1) that the following general formula (1) of the sulphur (B) of 1～10 mass parts and 0.1～10 mass parts represents and makes.
(in the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or divalent aromatic group.)
In the preference of rubber combination of the present invention, the compound of above-mentioned general formula (1) expression is the compound of following general formula (2) expression.
(in the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or divalent aromatic group.)
In addition, being characterized as of another rubber combination of the present invention, with respect to 100 mass parts rubber constituents (A), cooperate the composition (C2) of the sulphur (B) of 1～10 mass parts and 0.1～10 mass parts and make, wherein said composition (C2) is constructed as follows: the compound of above-mentioned general formula (2) expression of 60～100 weight %, expression and compound n=2 of the following general formula (3) of 0～20 weight %, expression and compound n=3 of the following general formula (3) of 0～10 weight % and expression and compounds n=4～6 (but said composition does not comprise that the compound of above-mentioned general formula (2) expression is the pure substance of 100 weight %) of following general formula (3) that total amount is 0～10 weight %.
(in the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or divalent aromatic group, and n represents 2～6 integer.)
Rubber combination of the present invention, preferably also containing the amount that aforementioned rubber constituent with respect to 100 mass parts is scaled cobalt is the organic acid cobalt salt of 0.03～1 mass parts.
In the preference of other of rubber combination of the present invention, aforementioned rubber constituent is by at least a formation in natural rubber and the polyisoprene rubber (IR).
In the preference of other of rubber combination of the present invention, aforementioned rubber constituent is made of the synthetic rubber of natural rubber (NR) more than the 50 quality % and surplus
In addition, the invention provides a kind of cementability improving agent, promptly, the 1st cementability improving agent of the present invention is characterized as the compound that contains above-mentioned general formula (2) expression, the 2nd cementability improving agent of the present invention is characterized as and contains a kind of composition, and expression and compounds n=4～6 of expression and compound n=3 of the above-mentioned general formula (3) of said composition expression and compound n=2,0～10 weight % by the above-mentioned general formula (3) of the compound of the above-mentioned general formula (2) of 60～100 weight % expression, 0～20 weight % and the above-mentioned general formula (3) that total amount is 0～10 weight % are formed.
And then, the present invention is airtyred to be characterized as: the belt portion that constitutes of the belt by more than one deck that has disposed cord body portion that is made of the casingply more than one deck and the tire radius direction that is provided in this cord body portion outside, at least one side in this cord body portion and the belt portion is contained the layer that steel wire cord constituted by the coating rubber that has been covered, and at least one side in cord body portion and the belt portion uses the coating rubber of above-mentioned rubber combination as the lining steel wire cord.
According to the present invention, a kind of rubber combination can be provided, in the time of processibility when this rubber combination keeps cooperating and high moisture-proof thermal bonding, the initial stage cementability of metal reinforcement materials such as inhibition and steel wire cord and the time dependent of moisture-proof thermal bonding change.
In addition, according to the present invention, a kind of pneumatic tyre can be provided, this pneumatic tyre is that at least one side is contained pneumatic tyre by steel wire cord constituted the layer of the coating rubber that has been covered in cord body portion and the belt portion, use the coating rubber of above-mentioned rubber combination by at least one side in cord body portion and belt portion as the lining steel wire cord, because the viscosity of this rubber combination is low, processibility height when so tire prepares, adhesion durability between steel wire cord and the coating rubber and bonding stability are high simultaneously, thereby pneumatic tyre of the present invention possesses high-durability.
Description of drawings
[Fig. 1] is the cross-sectional view of the airtyred example of the present invention.
Embodiment
Below the present invention will be described in detail.Being characterized as of rubber combination of the present invention, with respect to the rubber constituent of 100 mass parts, the compound of above-mentioned general formula (1) expression of the sulphur of cooperation 1～10 mass parts and 0.1～10 mass parts forms.
Rubber constituent as rubber combination of the present invention, get final product so long as have the material of caoutchouc elasticity, no particular restriction, except that natural rubber, can also use all known rubber such as synthetic rubber such as vinyl aromatic hydro carbons/conjugated diene copolymer, polyisoprene rubber, divinyl rubber, isoprene-isobutylene rubber, halogenated butyl rubber, ethylene-propylene rubber.This rubber constituent can be used alone, and also can mix use more than 2 kinds.From considering that with the adhesion properties of metal reinforcement material and the destruction characteristic aspect of rubber combination this rubber constituent is a synthetic rubber by at least a natural rubber and the surplus that constitutes or contain more than the 50 quality % in natural rubber and the polyisoprene rubber preferably.
The sulphur that cooperates in the rubber combination of the present invention is not had particular restriction, use powder usually.The use level of the sulphur that cooperates in the rubber combination of the present invention is with respect to 100 mass parts rubber constituents, in the scope of 1～10 mass parts, preferably in the scope of 3～8 mass parts.The use level of sulphur with respect to 100 mass parts rubber constituents when 1 mass parts is above, from considering it is preferred, when 10 mass parts are following, can suppress the generation of superfluous adhesive linkage with the cementability aspect of metal reinforcement material such as steel wire cord, so cementability can not reduce, therefore as preferred.
In the compound of above-mentioned general formula (1) expression that cooperates with rubber combination of the present invention, R represents that carbonatoms is 1～16 divalent aliphatic group or divalent aromatic group in the formula.As the compound of general formula (1) expression, for example can enumerate the compound of general formula (2) expression.The definition of R in R in the general formula (2) and the general formula (1) is identical.
Herein, it as carbonatoms 1～16 divalent aliphatic group, for example can enumerate, the alkylidene group of straight or brancheds such as methylene radical, ethylidene, butylidene, isobutylene, octylene, 2-ethyl hexylidene, the alkylene group of straight or brancheds such as vinylene (ethenylene group), 1, inferior octenyl, alkylidene group or alkylene group that the hydrogen atom of above-mentioned alkylidene group of replacement such as hydroxyl or amino or alkylene group obtains, alicyclic radicals such as cyclohexylidene.In addition, as the divalent aromatic group, can enumerate can substituted phenylene, can substituted naphthylidene etc.Wherein, if consider from the aspects of buying such as easiness, preferred carbonatoms is 2～10 alkylidene group and phenylene, preferred especially ethylidene, butylidene, octylene, phenylene.
As the concrete example of the compound of the general formula (1) that cooperates with rubber combination of the present invention expression, can enumerate propanedioic acid two (2-hydroxy phenyl) ester, succsinic acid two (2-hydroxy phenyl) ester, FUMARIC ACID TECH GRADE two (2-hydroxy phenyl) ester, maleic acid two (2-hydroxy phenyl) ester, oxysuccinic acid two (2-hydroxy phenyl) ester, methylene-succinic acid two (2-hydroxy phenyl) ester, citraconic acid two (2-hydroxy phenyl) ester, hexanodioic acid two (2-hydroxy phenyl) ester, tartrate two (2-hydroxy phenyl) ester, nonane diacid two (2-hydroxy phenyl) ester, sebacic acid two (2-hydroxy phenyl) ester, cyclohexane dicarboxylic acid two (2-hydroxy phenyl) ester, terephthalic acid two (2-hydroxy phenyl) ester, m-phthalic acid two (2-hydroxy phenyl) ester, propanedioic acid two (3-hydroxy phenyl) ester, succsinic acid two (3-hydroxy phenyl) ester, FUMARIC ACID TECH GRADE two (3-hydroxy phenyl) ester, maleic acid two (3-hydroxy phenyl) ester, oxysuccinic acid two (3-hydroxy phenyl) ester, methylene-succinic acid two (3-hydroxy phenyl) ester, citraconic acid two (3-hydroxy phenyl) ester, hexanodioic acid two (3-hydroxy phenyl) ester, tartrate two (3-hydroxy phenyl) ester, nonane diacid two (3-hydroxy phenyl) ester, sebacic acid two (3-hydroxy phenyl) ester, cyclohexane dicarboxylic acid two (3-hydroxy phenyl) ester, terephthalic acid two (3-hydroxy phenyl) ester, m-phthalic acid two (3-hydroxy phenyl) ester, propanedioic acid two (4-hydroxy phenyl) ester, succsinic acid two (4-hydroxy phenyl) ester, FUMARIC ACID TECH GRADE two (4-hydroxy phenyl) ester, maleic acid two (4-hydroxy phenyl) ester, methylene-succinic acid two (4-hydroxy phenyl) ester, citraconic acid two (4-hydroxy phenyl) ester, hexanodioic acid two (4-hydroxy phenyl) ester, tartrate two (4-hydroxy phenyl) ester, nonane diacid two (4-hydroxy phenyl) ester, sebacic acid two (4-hydroxy phenyl) ester, cyclohexane dicarboxylic acid two (4-hydroxy phenyl) ester, terephthalic acid two (4-hydroxy phenyl) ester, m-phthalic acid two (4-hydroxy phenyl) ester etc.
Wherein, preferred propanedioic acid two (3-hydroxy phenyl) ester, succsinic acid two (3-hydroxy phenyl) ester, FUMARIC ACID TECH GRADE two (3-hydroxy phenyl) ester, maleic acid two (3-hydroxy phenyl) ester, oxysuccinic acid two (3-hydroxy phenyl) ester, methylene-succinic acid two (3-hydroxy phenyl) ester, citraconic acid two (3-hydroxy phenyl) ester, hexanodioic acid two (3-hydroxy phenyl) ester, tartrate two (3-hydroxy phenyl) ester, nonane diacid two (3-hydroxy phenyl) ester, sebacic acid two (3-hydroxy phenyl) ester, cyclohexane dicarboxylic acid two (3-hydroxy phenyl) ester, terephthalic acid two (4-hydroxy phenyl) ester, m-phthalic acid two (4-hydroxy phenyl) ester, preferred especially succsinic acid two (3-hydroxy phenyl) ester, hexanodioic acid two (3-hydroxy phenyl) ester, sebacic acid two (3-hydroxy phenyl) ester, terephthalic acid two (4-hydroxy phenyl) ester, m-phthalic acid two (4-hydroxy phenyl) ester.
The preparation method of the compound of above-mentioned general formula (1) expression does not have special qualification, for example, the compound that can make two etherides of following general formula (4) expression and following general formula (5) expression alkali exist or non-existent condition under reaction and making.
(in the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or divalent aromatic group, and X represents halogen atom.)
The definition of R in R in the general formula (4) and the aforementioned formula (1) is identical, and X represents halogen atom.As halogen atom, preferred chlorine atom or bromine atoms.
Compound as general formula (4) expression, can enumerate, the malonyl-dichloro, the succinyl-dichloro, the fumaroyl dichloro, the maleoyl-dichloro, the glutaryl dichloro, adipyl chloride, the suberoyl dichloro, the azelaoyl dichloro, sehacoyl chloride, 1,10-decane two acyl dichloros, 1,12-dodecane two acyl dichloros, 1, aliphatics two acyl dichloros such as 16-n-Hexadecane two acyl dichloros, hexanaphthene two acyl dichloros, ester ring type two acyl dichloros such as tetrahydrobenzene two acyl dichloros, tere-phthaloyl dichloride, aromatic series two acyl dichloros such as isophthaloyl dichloro, the malonyl-dibromo, the succinyl-dibromo, the fumaroyl dibromo, the maleoyl-dibromo, the glutaryl dibromo, the hexanedioyl dibromo, the suberoyl dibromo, the azelaoyl dibromo, the sebacoyl dibromo, 1,10-decane two acyl dibromos, 1,12-dodecane two acyl dibromos, 1, aliphatics two acyl dibromos such as 16-n-Hexadecane two acyl dibromos, hexanaphthene two acyl dibromos, ester ring type two acyl dibromos such as tetrahydrobenzene two acyl dibromos, paraphenylene terephthalamide's dibromo, aromatic series two acyl dibromos such as isophthaloyl dibromo.Wherein preferred malonyl-dichloro, succinyl-dichloro, adipyl chloride, azelaoyl dichloro, sehacoyl chloride, tere-phthaloyl dichloride, isophthaloyl dichloro, malonyl-dibromo, succinyl-dibromo, hexanedioyl dibromo, azelaoyl dibromo, sebacoyl dibromo, paraphenylene terephthalamide's dibromo, isophthaloyl dibromo etc.
On the other hand, as the compound of general formula (5) expression, can enumerate pyrocatechol, Resorcinol and Resorcinol.
The alkali of use uses organic basess such as pyridine, beta-picoline, N-methylmorpholine, xylidine, Diethyl Aniline, Trimethylamine, triethylamine, tributylamine usually during as the compound reaction of the compound of general formula (4) expression and general formula (5) expression.
When the compound of the compound of general formula (4) expression and general formula (5) expression reacted, the compound of the compound of general formula (4) expression and general formula (5) expression reacted with 1: 4～1: 30 mol ratio usually.
When the compound of the compound of general formula (4) expression and general formula (5) expression reacts, can use solvent in order to make purposes such as material dissolution.As solvent, can directly use above-mentioned organic bases as solvent, also can use and not hinder other organic solvents that reaction is carried out.For example can enumerate ether solvents such as dimethyl ether ， diox as above-mentioned solvent.
Temperature of reaction when the compound of the compound of general formula (4) expression and general formula (5) expression reacts is generally-20 ℃～120 ℃.
The compound of general formula (1) expression that obtains according to previous reaction can separate from reaction mixture according to known method.That is, can enumerate following method: by operations such as underpressure distillation, distillation is removed the compound of the organic bases that is used for reacting and general formula (5) expression and the reaction organic solvent with an organic solvent the time and is made it the exsiccant method; The poor solvent of the compound of general formula (1) expression joined make it reppd method in the reaction mixture; With the water and the method etc. of not adding extraction organic layer in the reaction mixture to the miscible organic solvent of water.In addition, difference according to circumstances also can be made with extra care by recrystallization.
Poor solvent as the compound of aforementioned formula (1) expression makes water usually.In addition, as above-mentioned not miscible organic solvent, can use ester classes such as vinyl acetic monomer, N-BUTYL ACETATE, ketones such as methyl iso-butyl ketone (MIBK), diisobutyl ketone with water.
When using Resorcinol, can obtain the composition of forming as main component, by the compound of the compound of general formula (2) expression and general formula (3) expression with the compound of general formula (2) expression as the compound of general formula (5) expression.
The definition of R in R in the general formula (3) and the general formula (1) is identical, and n represents 2～6 integer.
For example, in the composition that the compound by the compound of general formula (2) expression and general formula (3) expression that obtains when using Resorcinol in the previous reaction is formed, the compound, the total amount that contain n=3 in the general formula (3) of compound, 0～10 weight % of n=2 in the general formula (3) of compound, 0～20 weight % of general formula (2) expression of 60～100 weight % usually are about the compound of the middle n=4 of general formula (3)～6 of 10 weight %.Can control above-mentioned ratio by the compound of change general formula (4) expression and the mol ratio of Resorcinol.
Aforementioned compound and the composition formed of the compound of general formula (3) the expression identical method of separation method that also can adopt the compound of representing with aforementioned formula (1) by general formula (2) expression separated from the reaction mixture that contains above-mentioned substance.
The compound of general formula (2) expression is when 60 weight % are above, with the damp and hot cementability raising of carrying out after rubber cooperates when bonding.Judge that from the viewpoint that improves damp and hot cementability the amount of the compound of general formula (2) expression is 70～100 weight % more preferably, further preferred 80～100 weight %.
When cooperating the compound of above-mentioned general formula (1) expression in the rubber combination of the present invention, the use level of the compound of general formula (1) expression, with respect to the rubber constituent of 100 mass parts in the scope of 0.1～10 mass parts, preferably in the scope of 0.3～6 mass parts.The use level of the compound of general formula (1) expression, when 0.1 mass parts is above, can improve the damp and hot cementability of rubber combination with respect to the rubber constituent of 100 mass parts, when 10 mass parts are following, can suppress the frosting of the compound of general formula (1) expression, so preferred above-mentioned scope.
In addition, when cooperating the composition of forming by the compound of the compound of above-mentioned general formula (2) expression and above-mentioned general formula (3) expression in the rubber combination of the present invention, the use level of said composition is with respect to 100 mass parts rubber constituents, in the scope of 0.1～10 mass parts, preferably in the scope of 0.3～6 mass parts.Compound with above-mentioned general formula (2) expression is the use level of the composition of main component, when 0.1 mass parts is above, can improve the damp and hot cementability of rubber combination with respect to the rubber constituent of 100 mass parts, when 10 mass parts are following, the compound that can suppress with above-mentioned general formula (2) expression is the frosting of the composition of main component, so preferred above-mentioned scope.
Can also cooperate the organic acid cobalt salt in the rubber combination of the present invention.As this organic acid cobalt salt, for example can enumerate: cobalt naphthenate, cobalt stearate, new cobalt decanoate, sylvic acid cobalt, tertiary monocarboxylic acid cobalt (versatic acid cobalt salt), cobalt tallate (tall oil acid cobalt salt) etc.This organic acid cobalt salt can be for replacing the formed composite salt of an organic acid part with boric acid etc.Particularly, can enumerate Manobond (trade mark: the OMG system) etc.As the use level of organic acid cobalt salt,, show preferred cooperation 0.03～1 mass parts with the cobalt scale with respect to the above-mentioned rubber constituent of 100 mass parts.The use level of organic acid cobalt salt, with respect to the rubber constituent of 100 mass parts, when 0.03 mass parts was above, the cementability between rubber combination and metal reinforcement material improved as the cobalt amount, can suppress the aging of rubber combination when 1 mass parts is following.
In rubber combination of the present invention, except that above-claimed cpd or composition, rubber constituent, sulphur, organic acid cobalt salt, can be according to use level commonly used Synergist S-421 95 commonly used in the compound rubber industry suitably, described Synergist S-421 95 is: methylene radical such as methoxymethyl melamine such as weighting agents such as carbon black and silicon-dioxide, fragrant wet goods tenderizer, vulkacit H, pentamethoxyl methylmelamine, hexa-methylene methylmelamine are supplied with body, vulcanization accelerator, sulfuration and are promoted auxiliary, anti-aging agent etc.The compound method of rubber combination of the present invention does not have particular restriction, for example, can use Banbury or roller etc., and above-claimed cpd or composition, sulphur, organic acid cobalt salt and various Synergist S-421 95 and rubber constituent is mixing, prepares.
The metal reinforcement material bonding with rubber combination of the present invention for can be bonding well with rubber, be preferably implemented electroplating processes with brass, zinc or the metal that wherein contains nickel or cobalt, especially preferably implements electroplating processes with brass.
In direct sulfuration when bonding, rubber combination of the present invention can significance ground improves cementability with the metal reinforcement material as the cementability improving agent.So, the compound and the following composition of above-mentioned general formula (2) expression are suitable as the cementability improving agent, expression and compound n=3 of the above-mentioned general formula (3) of described composition expression and compound n=2,0～10 weight % by the above-mentioned general formula (3) of the compound of the above-mentioned general formulas of 60～100 weight % (2) expression, 0～20 weight % and add up to expression and compounds n=4～6 of the above-mentioned general formula (3) of 0～10 weight % and form.
It is the composition of main component that the compound that cooperates in the rubber combination of the present invention reaches with this compound, compares with Resorcinol or RF resin, has to be easy to and rubber constituent blended characteristics.Therefore, cooperate this compound and be the rubber combination that the composition of main component obtains, compare, have the tendency that is difficult to frosting with the rubber combination that cooperates Resorcinol or RF resin to obtain with this compound.Infer that The above results is because the compound that cooperates in the rubber combination of the present invention and be that the polarity of composition of main component is lower than Resorcinol or RF resin with this compound.And then, no matter showing, rubber combination of the present invention changes all very stable cementability of little storage time length in time.
Then, with reference to diagram pneumatic tyre of the present invention is elaborated.Fig. 1 is the cross-sectional view of an airtyred example of the present invention, among the figure, and 1 expression fetus face, the pair of sidewall portion that 2 expressions are extended to the radial direction inboard from the side of fetus face 1, the inner bead part that links to each other of the radial direction of 3 expressions and sidewall portion 2.
Herein, the cord body portion 4 of the skeleton structure of formation tire, above-mentioned each one 1,2,3 of fortified tyre, constitute by the casingply more than one deck, and have body and turnup, described body extend into along toroidal direction between each bead core 5 that is configured in respectively in each bead part 3, described in bag portion each bead core 5 periphery from the inboard of tire width direction laterally outside radial direction direction roll.Cord body portion 4 among the figure is made of one deck casingply, but the sheet number of cord body can be multi-disc in tire of the present invention.
In addition, 6 expression belt portions among the figure, belt portion 6 is made of the belt more than one deck of configuration outside the tire radius direction of cord body portion 4 crown parts.Belt 6 among the figure is made of two-layer belt, but the sheet number of belt has more than and is limited to this in tire of the present invention.
At least one side in this airtyred cord body portion 4 and the belt portion 6 contains the steel-cord ply of useful coating rubber-coated.That is, if in the casingply of cord body portion 4 at least in the belt of one deck and/or belt portion 6 at least one deck be steel-cord ply, also can one deck above casingply and the belt more than one deck be steel-cord ply.
Among at least one side in cord body portion 4 and belt portion 6, use above-mentioned rubber combination herein, as the used coating rubber of lining steel wire cord.Because among at least one side in constituting the present invention airtyred cord body portion and belt portion, use the coating rubber of above-mentioned rubber combination, so processibility height and weather resistance height when this tire prepares as its steel-cord ply.
With above-claimed cpd or with it is composition, sulphur, organic acid cobalt salt and the various Synergist S-421 95s etc. and the mixing preparation formation of above-mentioned rubber constituent composition of main component, with roller etc. said composition is processed into sheet, under the state of the sheet rubber clamped wire cord that 2 processing obtain, carry out machine-shaping then, form cord body portion or belt portion.According to method commonly used with the belt lamination that forms in the tire radius direction outside of cord body portion, constitute pneumatic tyre of the present invention with other parts.Airtyred fetus face of the present invention, sidewall portion and bead part etc. can suitably adopt material, shape, the configuration of using in the above-mentioned part of common tire.
With the mutually bonding steel wire cord of rubber combination that uses among at least one side of the present invention airtyred cord body portion and belt portion, for can be bonding with rubber well, preferably implemented the steel wire cord of electroplating processes, especially preferably implemented the steel wire cord of electroplating processes with brass with brass, zinc or the metal that contains nickel, cobalt among both.In addition, the size of this steel wire, twisting count, twisted condition etc. can suitably be selected according to the performance that requires of tire.
＜embodiment 〉
Below, enumerate embodiment the present invention is done more detailed explanation, but the present invention is not limited to following embodiment.
(preparation example 1)
The solution that 330.6g (3.0mol) Resorcinol is dissolved in the 600.0g pyridine and forms places ice bath, and temperature is remained on below 15 ℃, simultaneously 54.9g (0.30mol) hexanedioyl chlorine slowly is added drop-wise in this solution.Make the reaction mixture of gained rise to room temperature after dripping end, place 1 and finish reaction round the clock.Under reduced pressure pyridine distilled from reaction mixture and remove, 1200g water is joined in the residue, precipitation is separated out in the ice bath cooling.With the sedimentation and filtration of separating out, wash with water, with the wet body drying under reduced pressure of gained, obtain 84g white～flaxen powder.Utilization is equipped with separation and Extraction to handle this powder with the liquid chromatography of device by following condition, and separation and Extraction obtains containing the elutriant of main component.This elutriant is concentrated, and the crystallization that filtered and recycled is separated out obtains fusing point and is 140～143 ℃ crystallization behind the drying under reduced pressure.Analytical results shows that this crystallization is hexanodioic acid two (3-hydroxy phenyl) ester.
Separation and Extraction is as follows with the HPLC condition.
Chromatographic column: Shim-pack PREP-ODS (Shimadzu Seisakusho Ltd.'s system)
Column temperature: 25 ℃
Elutriant: methanol mixed solvent (85/15 (W/W%))
Eluent flow rate: flow 3ml/ branch
Detector: UV detector (254nm)
In addition, the appraising datum of hexanodioic acid two (3-hydroxy phenyl) ester is as follows.
The MS spectroscopic data
EI(Pos.)m/z＝330
The IR spectroscopic data
3436cm
-1: hydroxyl
2936cm
-1: alkyl
1739cm
-1: ester group
The NMR spectroscopic data is shown in table 1-1 and table 1-2.
Table 1-1 table 1-2
(preparation example 2)
Obtain the 84g powder according to the reaction identical with preparation example 1, with HPLC this powder is analyzed, the result shows that hexanodioic acid two in this powder (3-hydroxy phenyl) ester is 89 weight %.In addition, also contain in the powder: compound, the 2 weight % stock yard dihydroxy-benzenes of n=3 in the compound of the compound of n=2, the following formulas of 2 weight % (6) expression in the compound of the following formulas of 7 weight % (6) expressions (below, be also referred to as oligopolymer sometimes).In addition, with LC-MS the compound of following formula (6) expression is identified.
MS spectrographic condition determination is as follows.
Mass range: 200～2000amu (1.98+0.02sec)
Ionization method: ESI (electron spray(ES))
Pattern (Mode): just
Capillary voltage (Capilary): 3.15KV
Taper hole voltage (Cone): 35V
Source temperature (S.B.Tmp.): 150 ℃
Precipitation temperature (Deslv.tmp): 400 ℃
Multiplier voltage (Multi): 650V
N
2： 750L/hr
n＝2：?551.1[M+H]+、568.2[M+NH
4]+
n＝3：?771.2[M+H]+、788.2[M+NH
4]+
n＝4：?1008.3[M+NH
4]+
n＝5：?1228.3[M+NH
4]+
In addition, the analysis condition of HPLC is as follows.
1, the analysis of hexanodioic acid two (3-hydroxy phenyl) ester, Resorcinol
Chromatographic column: the A-312ODS of YMC society
Column temperature: 40 ℃
Elutriant: methanol=7/3 (transferring pH=3) with phosphoric acid
Detect: UV (254nm)
2, the analysis of oligopolymer
Chromatographic column: the A-312ODS of YMC society
Column temperature: 40 ℃
Elutriant: acetonitrile/water=8/2 (transferring pH=3.5) with acetic acid
Detect: UV (254nm)
(preparation example 3)
Except that using 176.2g (1.6mol) Resorcinol, 400g pyridine, 73.2g (0.4mol) hexanedioyl chlorine, carry out and preparation example 1 identical operations, obtain the 118.6g powder.The HPLC analytical results shows, contains compound, the 2.9 weight % stock yard dihydroxy-benzenes of n=5 of compound, the aforementioned formula of 0.2 weight % (6) expression of n=4 of compound, the aforementioned formula of 0.8 weight % (6) expression of n=3 of compound, the aforementioned formulas of 3.0 weight % (6) expression of the n=2 of 73.4 weight % hexanodioic acid two (3-hydroxy phenyl) esters, the aforementioned formulas of 13.9 weight % (6) expression in the powder.
(preparation example 4)
440.4g (4.0mol) Resorcinol is dissolved in the solution that forms in the pyridine of 405.0g places ice bath, temperature remains on below 15 ℃, simultaneously 62.0g (0.4mol) succinyl-dichloro slowly is added drop-wise in this solution.After dripping end the gained reaction mixture is risen to room temperature, place 1 and finish reaction round the clock.Pyridine is removed in distillation from reaction mixture under reduced pressure, adds 1800g water in residue, and ice bath cooling back liquid all becomes white casse and is divided into two-layer.In oil reservoir, add 200g water and 600g vinyl acetic monomer, extract.Behind the organic layer usefulness cold water washing of gained 5 times, use dried over mgso.Afterwards 500g toluene is added to distillation and remove in the dope of gained behind the vinyl acetic monomer, make it crystallization, filtration,, carry out slurryization 2 times with 1L water with after the toluene wash.After the wet body of gained is dissolved in 100g methyl alcohol, adds 1L water and make it redeposition, after filtration, washing, drying, obtain the faint yellow powder of 82.3g.The HPLC analytical results shows that the main component of powder is the composition that is equivalent to 91.0 area %.In addition, the Resorcinol that contains 0.7 weight % in this powder.The result of structural analysis can judge that main component is succsinic acid two (3-hydroxy phenyl) ester in the powder.
In addition, the appraising datum of succsinic acid two (3-hydroxy phenyl) ester is as follows.
The MS spectroscopic data
EI(Pos.)m/z＝302
The IR spectroscopic data
3361cm
-1: hydroxyl
2984cm
-1: alkyl
1732cm
-1: ester group
The NMR spectroscopic data is shown in table 2-1 and table 2-2.
Table 2-1 table 2-2
(preparation example 5)
330.3g (3.0mol) Resorcinol is dissolved in the solution that forms in the pyridine of 303.7g places ice bath, temperature remains on below 15 ℃, simultaneously 71.7g (0.3mol) sehacoyl chloride slowly is added drop-wise in this solution.After dripping end the gained reaction mixture is risen to room temperature, place 1 and finish reaction round the clock.Under reduced pressure pyridine distilled from reaction mixture and remove, add 250g water in residue, precipitation is separated out in the ice bath cooling.Filter, wash the precipitation of separating out with water, the wet body that obtains is carried out drying under reduced pressure, obtain 102.8g white～faint yellow powder.The HPLC analytical results shows that the main component of powder is the composition that is equivalent to 98.7 area %.In addition, contain 0.2 weight % Resorcinol in this powder.Results of structural analysis judges that the main component in the powder is sebacic acid two (3-hydroxy phenyl) ester.
In addition, the appraising datum of sebacic acid two (3-hydroxy phenyl) ester is as follows.
The MS spectroscopic data
EI(Pos.)m/z＝386
The IR spectroscopic data
3380cm
-1: hydroxyl
3000～2800cm
-1: chain alkyl
1732,1749cm
-1: ester group
The NMR spectroscopic data is shown in table 3-1 and table 3-2.
Table 3-1 table 3-2
(preparation example 6)
440.4g (4.0mol) Resorcinol is dissolved in the solution that forms in the pyridine of 405g places ice bath, temperature remains on below 15 ℃, and the suspension liquid that simultaneously 81.2g (0.4mol) tere-phthaloyl dichloride is dissolved in gained in the 180g toluene slowly is added drop-wise in the above-mentioned solution.After dripping end the gained reaction mixture is risen to room temperature, place 1 and finish reaction round the clock.Under reduced pressure pyridine distilled from reaction mixture and remove, residue is put cold back and is generated precipitation.Add 300g water and make it outstanding turbid, be disposed in the 1L water, filter, wash with water the precipitation of separating out, the wet body that obtains is carried out drying under reduced pressure, obtain 130.0g colour of camel's hair powder.The HPLC analytical results shows that the main component of powder is the composition that is equivalent to 90.7 area %.In addition, contain 0.2 weight % Resorcinol in this powder.Results of structural analysis judges that the main component in the powder is terephthalic acid two (3-hydroxy phenyl) ester.
(preparation example 7)
440.4g (4.0mol) Resorcinol is dissolved in the solution that forms in the pyridine of 405g places ice bath, temperature remains on below 15 ℃, and the suspension liquid that simultaneously 81.2g (0.4mol) isophthaloyl dichloro is dissolved in gained in the 80g toluene slowly is added drop-wise in the above-mentioned solution.After dripping end the gained reaction mixture is risen to room temperature, place 1 and finish reaction round the clock.Under reduced pressure pyridine distilled from reaction mixture and remove, residue is put cold back and is generated precipitation.Add 500g water, the ice bath cooling makes it aging down, after filtration, washing obtains the body that wets.The wet body that obtains is dissolved in the methanol solution of 200g, is disposed in the 2L water, filter, wash with water the precipitation of separating out, the wet body that obtains is carried out drying under reduced pressure, obtain 130.2g colour of camel's hair powder.The HPLC analytical results shows that the main component of powder is the composition that is equivalent to 89.4 area %.In addition, contain 0.8 weight % Resorcinol in this powder.Results of structural analysis judges that the main component in the powder is m-phthalic acid two (3-hydroxy phenyl) ester.
(embodiment 1～9)
Use the Banbury of 2200ml, with in the preparation example 1～7 preparation composition as test compound, cooperate the mixing mixing of prescription according to the rubber shown in the table 4, prepare unvulcanized rubber combination, measure frost-resistance, mooney viscosity (Mooneyviscosity), cooperate the cementability after cementability when just having finished and compound rubber are placed in order to following method, and estimate.The result is as shown in table 4.
(1) frost-resistance
Down storage is after 7 days at 40 ℃ with unvulcanized rubber combination, and range estimation confirms whether Synergist S-421 95 separates out at rubber surface, with zero, △, * judge.
Zero: Synergist S-421 95 is not separated out on the surface
△: part is separated out
*: Synergist S-421 95 is separated out on whole surface
(2) mooney viscosity
Measure 130 ℃ of the ML (1+4) of unvulcanized rubber combination according to JIS K6300-2001.The low more result that shows is good more for numerical value.
(3) adhesive test (rubber combination)
To be electroplate with brass (Cu:63 quality %, Zn:37 quality %) steel wire cord (1 * 5 structure, single steel wire footpath 0.25mm) arranges with the spaced and parallel of 12.5mm, this steel wire cord is applied from both sides up and down with each rubber combination, under 160 ℃ * 15 minutes condition, vulcanize at once afterwards, prepare the sample of wide 12.5mm.For following each cementability is benchmark with ASTM-D-2229, and steel wire cord is extracted out from each sample, and the lining state of visual observations rubber is represented with 0～100%, as the index of each cementability.The big more ecbatic of numerical value is good more.The initial stage cementability is measured after aforementioned sulfuration immediately.Damp and hot cementability makes it to measure after aging under 70 ℃, humidity 100%RH, 4 days wet heat condition after aforementioned sulfuration.
(4) bonding stability test (rubber combination)
To be coated with the steel wire cord-rubber combined body of the not sulfided state that aforementioned steel wire cord obtains with each rubber combination from both sides up and down, in the constant temperature and humidity cabinet of 40 ℃ * 80RH%, place after 7 days, under 160 ℃ * 15 minutes condition, vulcanize, mensuration initial stage cementability is as the index of bonding stability.
(comparative example 1)
Compound that obtains in not using above-mentioned preparation example and composition similarly cooperate with embodiment as the test compound, and the preparation rubber combination is estimated.The result is as shown in table 4.
(comparative example 2)
Except that in the rubber basic recipe, cooperate 2 mass parts Resorcinols as test compound, similarly cooperate with embodiment, the preparation rubber combination is estimated.The result is as shown in table 4.
(comparative example 3)
Except that in the rubber basic recipe, cooperate 2 mass parts RF resins as test compound, similarly cooperate with embodiment, the preparation rubber combination is estimated.The result is as shown in table 4.Need to prove that the RF resin prepares as follows.
At first, 1100g water, 1100g (10mol) Resorcinol, 1.72g (10mmol) tosic acid put into be furnished with prolong, in the 4 neck flasks of whipping appts, thermometer, dropping funnel, nitrogen ingress pipe, be warming up to 70 ℃.Drip 37% formaldehyde solution of 477g (5.9mol) through 2 hours, kept 5 hours under this temperature, finish reaction.After reaction finishes, add in the 4g10% aqueous sodium hydroxide solution and after, change condenser into Dean-Stack type reflux exchanger, dephlegmate branch limit, limit is warming up to 150 ℃, removes moisture through 1 hour again under the reduced pressure of 20mmHg, obtains the RF resin.The softening temperature of gained RF resin is 124 ℃, and the amount of residual Resorcinol is 17%.
(comparative example 4)
The composition that in the rubber compounding of embodiment 1, cooperating 12 mass parts preparation examples 2, prepares as test compound, cooperate similarly to Example 1, the preparation rubber combination is estimated similarly to Example 1.The result is as shown in table 4.
(comparative example 5)
Except that in the rubber basic recipe, cooperating 2 mass parts spies to open the disclosed mixed polyester of flat 7-118621 communique as test compound, similarly cooperate with embodiment in addition, the preparation rubber combination is estimated.The result is as shown in table 4.Need to prove that mixed polyester synthesizes according to the embodiment 1 that puts down in writing in the above-mentioned patent.
108.9g (0.99mol) Resorcinol, 131.4g (0.90mol) hexanodioic acid, 222.0g (2.175mol) acetic anhydride and 0.54g pyridine (is 0.5 weight % with respect to Resorcinol) are joined in the 4 neck flasks of the 300ml that is furnished with reflux exchanger and thermometer; after charging into nitrogen; stirred 15 minutes under the room temperature; be warming up to 100 ℃ afterwards, synthermal acetylize down 2 hours.Afterwards, the limit is distilled from system and is removed side reaction product acetic acid limit and be warming up to 140 ℃ of slakings 1 hour, is warming up to 240 ℃ of slakings 2 hours again.Then, under decompression (50mmHg), 240 ℃ condition, continue slaking.Reaction mixture is put in the evaporating dish, obtains the yellowish-brown sugar colour shape of 195.6g thing.Make it slowly crystallization with glass stick is mixing.Analytical results shows, contains 0.1 weight % Resorcinol, 0.5 weight % resorcin monoacetate, 0.8 weight % resorcin diacetate.In addition, the result with the GPC determining molecular weight is about 30000 (being converted into PS) of weight-average molecular weight.
As known from Table 4, the rubber combination frost-resistance excellence of embodiment, initial stage cementability and bonding stability are high, in addition, compare damp and hot cementability with comparative example 1 and improve significantly.
On the other hand, the rubber combination frost-resistance of comparative example 2 that contains Resorcinol is poor, and the increasing degree of comparing mooney viscosity with comparative example 1 is big, and bonding in addition stability is also very low.In addition, it is poor that rubber combination and the embodiment that contains the comparative example 3 of RF resin compares frost-resistance, and big with respect to the increasing degree of comparative example 1 mooney viscosity, not only damp and hot in addition cementability is low, and bonding stability is also very low.And then, the rubber combination of the comparative example 5 of cooperation mixed polyester, big with respect to the increasing degree of comparative example 1 mooney viscosity, damp and hot in addition cementability is also very low.
In addition, contain the rubber combination of the comparative example 4 of the composition for preparing in the 12 mass parts preparation examples 2, to compare frost-resistance poor with embodiment, and big with respect to the increasing degree of comparative example 1 mooney viscosity, compare bonding stability with embodiment also very poor.So the use level of above-mentioned composition is very necessary in the scope of 0.1～10 mass parts with respect to the rubber constituent of 100 mass parts.
Then, rubber combination coating steel wire cord with by above-mentioned preparation forms belt, passes through common method, trial-production is furnished with radial this belt, that be of a size of 185/70R14, and the cementability of steel wire cord and coating rubber is estimated as follows in this tire belt.Its result is as shown in table 5 with cooperating of used rubber combination.
(5) damp and hot cementability evaluation (tire)
After supplying the examination tire in the constant temperature and humidity cabinet of 100 ℃ of maintenances, 95%RH, to place for 5 weeks, belt is taken out from tire, steel wire cord in the belt stretches by the speed of tensile testing machine with 50mm/min, the lining state of the rubber of the steel wire cord that visual observations is exposed, with 0～100% its lining rate of expression, as the index of damp and hot cementability.The big more expression cementability of numerical value is good more.
(6) bonding estimation of stability (tire)
Tire base after the moulding is vulcanized after placing 7 days under 40 ℃, 80%RH, from this vulcanized tyre, take out belt, steel wire cord in the belt stretches by the speed of tensile testing machine with 50mm/min, the lining state of the rubber of the steel wire cord that visual observations is exposed, with 0～100% its lining rate of expression, as the index of bonding stability.
As known from Table 5, use contains the rubber combination of Resorcinol or RF resin as the tire in the comparative example 2 or 3 of the coating rubber of belt, compare damp and hot cementability with the tire of comparative example 1 and improve, but with the mooney viscosity increasing degree of the rubber combination of making coatings rubber greatly, poor, the bonding stability of frost-resistance is low.In addition, use the rubber combination that is combined with mixed polyester as the tire in the comparative example 5 of the coating rubber of belt, damp and hot cementability is insufficient.
On the other hand, use is combined with rubber combination that the composition for preparing in the preparation example obtains as the tire among the embodiment of the coating rubber of belt, compare with the tire of comparative example 1, can suppress the increase of mooney viscosity, and improve damp and hot cementability and bonding stability.
In addition, from the result of embodiment 2～4 and comparative example 4 as can be known, increase along with the use level of the composition for preparing in the preparation example, the tendency that mooney viscosity strengthens, processibility reduces that has rubber combination, so, the use level of the composition for preparing in the preparation example is very necessary in the scope of 0.1～10 mass parts with respect to the rubber constituent of 100 mass parts.
Claims (11)
1, a kind of rubber combination, described rubber combination are the rubber constituents with respect to 100 mass parts, and the compound of following general formula (1) expression of the sulphur of cooperation 1～10 mass parts and 0.1～10 mass parts forms,
In the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or phenylene, naphthylidene.
2, rubber combination as claimed in claim 1, wherein, the compound of described general formula (1) expression is the compound of following general formula (2) expression,
In the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or phenylene, naphthylidene.
3, rubber combination as claimed in claim 2, wherein, the R in the described general formula (2) is the alkylidene group or the phenylene of carbonatoms 2～10.
4, a kind of rubber combination, described rubber combination is the rubber constituent with respect to 100 mass parts, the composition of the sulphur of cooperation 1～10 mass parts and the following composition of 0.1～10 mass parts forms: the compound of the described general formula of the claim 2 of 60～100 weight % (2) expression, expression and compound n=2 of the following general formula (3) of 0～20 weight %, expression and compound n=3 of the following general formula (3) of 0～10 weight % and expression and compounds n=4～6 of following general formula (3) that total amount is 0～10 weight %
In the formula, R represents that carbonatoms is 1～16 divalent aliphatic group or phenylene, naphthylidene, and n represents 2～6 integer.
5, rubber combination as claimed in claim 4, wherein, the R in described general formula (2) and the described general formula (3) is the alkylidene group or the phenylene of carbonatoms 2～10.
6,, wherein, also contain the organic acid cobalt salt that the amount that is scaled cobalt is 0.03～1 mass parts with respect to the aforementioned rubber constituent of 100 mass parts as each described rubber combination in the claim 1,2,4.
7, rubber combination as claimed in claim 6 is characterized by, and described rubber constituent is made of at least a in natural rubber and the polyisoprene rubber.
8, rubber combination as claimed in claim 7, wherein, described rubber constituent is made of the natural rubber more than the 50 quality % and the polyisoprene rubber of surplus.
9, a kind of cementability improving agent, described cementability improving agent contain the compound of the described general formula of claim 2 (2) expression.
10, a kind of cementability improving agent, described cementability improving agent contains following composition, the consisting of of described composition: the compound of the described general formula of the claim 2 of 60～100 weight % (2) expression, the described general formula of claim 4 (3) of 0～20 weight % is expression and the described general formula of claim 4 (3) of compound n=2,0～10 weight % is expression and compound n=3 and expression and compounds n=4～6 of the described general formula of claim 4 (3) that total amount is 0～10 weight %.
11, a kind of pneumatic tyre, described pneumatic tyre has disposed the cord body portion that is made of the cord body more than one deck and has been provided in the belt portion that the belt by more than one deck in the tire radius direction outside of described cord body portion constitutes, at least one side in this cord body portion and the belt portion is contained by the layer that constitutes with the rubber-covered steel wire cord of coating, it is characterized by, at least one side in cord body portion and the belt portion uses the coating rubber of each described rubber combination of claim 1～8 as the lining steel wire cord.
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| JP070663/2004 | 2004-03-12 | ||
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