JPH11286575A - Diene-based polymer composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition with highly dispersed silica, crosslinkable rapidly, hard to cause scorching, and capable of giving tires with excellent mechanical strength characteristics, high resistance to electrification and good fuel economy, by compounding a polar group-contg. diene-based rubber, silica as a reinforcing agent, a polyether-based polymer, a silane coupling agent and a silylating agent. SOLUTION: This composition comprises (A) a rubber component consisting mainly of a polar group-contg. diene-based rubber, (B) a reinforcing agent (pref. white carbon manufactured by wet process), including silica, (C) a polyether- based polymer, (D) a silane coupling agent, and (E) a silylating agent (pref. phenyltriethoxysilane), wherein the component A is composed pref. of 50-85 wt.% of a conjugated diene monomer unit, 0.1-10 wt.% of a polar group-contg. vinyl monomer unit, and 19.9-44.9 wt.% of an aromatic vinyl monomer unit, and the component C is pref. a copolymer of ethylene oxide or propylene oxide and allyl glycidyl ether.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polymer having a high crosslinking rate,
The present invention relates to a rubber composition which hardly generates scorch, has excellent strength properties, and provides an automobile tire having excellent fuel efficiency.

[0002]

2. Description of the Related Art In recent years, as resource saving and environmental measures have been emphasized, the demand for lower fuel consumption of automobiles has become more severe. Is required to contribute. In order to reduce the rolling resistance of the tire, a rubber material capable of providing a heating rubber having low heat generation is generally used as the rubber material for the tire.

Hitherto, it has been proposed to reduce the heat build-up by using a rubber composition obtained by mixing a diene rubber as a rubber material for a tire and silica as a reinforcing agent in place of carbon black in place of carbon black. However, compared with the carbon black-containing rubber composition, the silica-containing rubber composition has a problem that sufficient wear resistance and tensile strength cannot be obtained. It is considered that one of the causes is that a sufficient reinforcing effect cannot be exhibited because the affinity of silica for the diene rubber is lower than that of carbon black.

Hitherto, in order to increase the affinity between silica and a diene rubber, a method using a silane coupling agent has been proposed (JP-A-3-252431, JP-A-3-252433, etc.). ). However, in this method, it is necessary to use a large amount of an expensive silane coupling agent in order to achieve a sufficient effect.

As another improvement method, use of a diene rubber into which a substituent having an affinity for silica is introduced has been studied. For example, in a diene rubber obtained by an emulsion polymerization method, a diene rubber having a tertiary amino group introduced therein (Japanese Patent Laid-Open No.
No. 101344), and an alkylsilyl group (Japanese Unexamined Patent Publication No.
No. 88501), a diene rubber into which a halogenated silyl group (for example, JP-A-5-230286) or a substituted amino group (for example, JP-A-64-22940) is introduced.

However, most of the conjugated diene rubbers into which these substituents have been introduced are strongly coagulated with silica when mixed with silica, resulting in poor dispersion, resulting in poor processability, heat build-up, tensile strength and tensile strength. There is a disadvantage that properties such as abrasion resistance are not sufficiently improved.

[0007] Disperse silica well, processability, heat generation,
In order to improve properties such as tensile strength and abrasion resistance, it has been proposed to use a conjugated diene rubber obtained by copolymerizing a monomer containing a polar group. However, since the main structure contains a polar group, stability over time is insufficient, gelation is easily caused, and Mooney viscosity increases at a high temperature. Therefore, there is a problem that handling becomes difficult, for example, when the reinforcing agent such as silica is mixed by kneading, the reinforcing agent cannot be kneaded well, or the workability is reduced due to high viscosity.

[0008] In addition, conjugated diene-aromatic vinyl compound copolymer rubber containing silica has a low crosslinking rate, and is generally used with a sulfenamide-based crosslinking accelerator such as N-cyclohexyl-2-benzothiazolesulfenamide. The crosslinking speed is increased by using a guanidine-based crosslinking accelerator such as diphenylguanidine in combination. However, there is a problem that scorch is easily generated in the crosslinking using this crosslinking accelerator in combination. In recent years, a silylating agent has been added to a rubber containing silica, and a hydroxyl group, an amino group,
It has been proposed to increase the water repellency or improve the dispersibility of silica by making a hydrophilic portion having active hydrogen such as a carboxyl group hydrophobic, for example (see, for example, JP-A-7-118452, No. Hei 9-77915).

Furthermore, silica is non-conductive, while carbon black, a typical filler, is conductive. Therefore, the silica compound rubber product has a problem that static electricity generated by friction or the like is easily charged. As a solution, it has been proposed to blend both a silica and a polyether-based polymer into a diene-based rubber to impart conductivity to a crosslinked product of the silica-containing diene-based rubber composition to prevent electrification (for example, , PCT / JP97 / 013
No. 33 publication). However, there is no known example of mixing a silylating agent into this silica-containing diene rubber composition,
It was not known what crosslinked product would be obtained when a silylating agent was blended and crosslinked.

[0010]

DISCLOSURE OF THE INVENTION An object of the present invention is to disperse silica well, have a high crosslinking speed, hardly generate scorch, have excellent strength properties, are hardly charged, and have a low fuel consumption when used in tire materials. An object of the present invention is to provide a rubber composition capable of producing a tire having excellent properties.

[0011]

The present inventors have conducted intensive studies to overcome the above-mentioned problems of the prior art, and as a result, have found that diene rubbers containing a polar group, silica, polyether polymers and silanes. A rubber composition containing a coupling agent and a silylating agent is excellent in dispersibility of silica, has a high crosslinking rate, hardly generates scorch, has excellent strength properties, is hardly charged, and has a low level when used in tire materials. The inventors have found that the fuel efficiency is excellent, and have completed the present invention.

Thus, according to the present invention, (a) a rubber component having a polar group-containing diene rubber as a main component, (b) a reinforcing agent containing silica, (c) a polyether polymer,
There is provided a diene rubber composition containing (d) a silane coupling agent and (e) a silylating agent.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION (Polar group-containing diene rubber) The polar group-containing diene rubber used in the present invention is a conjugated diene monomer, a polar group-containing monomer copolymerizable with a conjugated diene monomer, and It is a copolymer rubber of a monomer which does not contain a polar group copolymerizable with these monomers as required.

As the conjugated diene monomer, for example, 1,
3-butadiene, 2-methyl-1,3-butadiene,
2,3-dimethyl-1,3-butadiene, 2-chloro-
Examples thereof include 1,3-butadiene and 1,3-pentadiene. Among these, 1,3-butadiene, 2-methyl-1,3-butadiene and the like are preferable, and 1,3-butadiene is more preferable. These conjugated dienes can be used alone or in combination of two or more.

The polar group-containing monomer other than the conjugated diene monomer and copolymerizable with the conjugated diene monomer is not particularly limited, but a polar group-containing vinyl monomer having a hetero atom is exemplified. .

The polar group-containing vinyl monomer having a hetero atom (hereinafter referred to as a polar group-containing vinyl monomer) is a polymerizable monomer having at least one polar group having a hetero atom in a molecule. If it is, there is no particular limitation. The hetero atom refers to an atom belonging to the second to fourth periods of the periodic table and belonging to the 5B group or the 6B group, and specifically includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, and the like. Is mentioned. Among them, nitrogen atom,
An oxygen atom and the like are preferable, and a nitrogen atom is particularly preferable. Specific examples of the polar group containing a hetero atom, for example,
Hydroxyl group, oxy group, epoxy group, carboxyl group, carbonyl group, oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group,
Thiocarbonyl group, imino group, amino group, nitrile group,
Examples include an ammonium group, an imide group, an amide group, a hydrazo group, an azo group, and a diazo group. Among these, hydroxyl group, oxy group, epoxy group, sulfide group,
Disulfide groups, imino groups, amino groups and the like are preferred,
A hydroxyl group, an amino group, an oxy group and the like are more preferred, and an amino group is even more preferred.

Examples of the polar group-containing vinyl monomer having a hetero atom include an amino group-containing vinyl monomer, a hydroxyl group-containing vinyl monomer, and an oxy group-containing vinyl monomer. A hydroxyl group-containing vinyl monomer, an amino group-containing vinyl monomer and the like are preferable, and an amino group-containing vinyl monomer is particularly preferable. These polar group-containing vinyl monomers can be used alone or in combination of two or more.

Examples of the amino group-containing vinyl monomer include a polymerizable monomer having at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among these, a tertiary amino group-containing vinyl monomer is particularly preferred.

Examples of the primary amino group-containing vinyl monomer include acrylamide, methacrylamide, p
-Aminostyrene, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) acrylate and the like.

Examples of the secondary amino group-containing vinyl monomer include, for example, anilinostyrenes disclosed in JP-A-61-130355;
Anilinophenylbutadienes disclosed in No. 56 and the like; N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N-mono such as N- (4-anilinophenyl) methacrylamide Substituted (meth) acrylamides; and the like.

Examples of the tertiary amino group-containing vinyl monomer include N, N-disubstituted aminoalkyl acrylate, N, N-disubstituted aminoalkylacrylamide,
An N, N-disubstituted amino aromatic vinyl compound, a vinyl compound having a pyridyl group and the like can be mentioned. Among these, N, N-disubstituted aminoalkyl acrylate, N, N
-Disubstituted aminoalkylacrylamides are preferred.

Examples of the N, N-disubstituted amino acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth)
Acrylate, N, N-dimethylaminobutyl (meth)
Acrylate, N, N-diethylaminoethyl (meth)
Acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate N, N-dibutylaminoethyl (meth) acrylate, N, N-dibutylaminopropyl (meth) acrylate, N, N-dibutylaminobutyl (meth) acrylate, N, N-dihexylaminoethyl (meth) acrylate, N And esters of acrylic acid or methacrylic acid such as N, N-dioctylaminoethyl (meth) acrylate and acryloylmorpholine. Among them, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) Acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate and the like are preferred.

Examples of the N, N-disubstituted aminoalkylacrylamide include N, N-dimethylaminomethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) ) Acrylamide, N, N-dimethylaminobutyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-diethylaminobutyl (meth) acrylamide, N- Methyl-N-ethylaminoethyl (meth) acrylamide,
N, N-dipropylaminoethyl (meth) acrylamide, N, N-dibutylaminoethyl (meth) acrylamide, N, N-dibutylaminopropyl (meth) acrylamide, N, N-dibutylaminobutyl (meth) acrylamide, N , N-Dihexylaminoethyl (meth)
Acrylamide compounds such as acrylamide, N, N-dihexylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide; and methacrylamide compounds. Among them, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like are preferable.

Examples of the N, N-disubstituted amino aromatic vinyl compound include N, N-dimethylaminoethylstyrene, N, N-diethylaminoethylstyrene, N, N
And styrene derivatives such as -dipropylaminoethylstyrene and N, N-dioctylaminoethylstyrene.

Examples of the vinyl compound having a pyridyl group include 2-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-
2-vinylpyridine and the like. Among them, 2-vinylpyridine, 4-vinylpyridine and the like are preferable.

Examples of the hydroxyl group-containing vinyl monomer include a polymerizable monomer having at least one primary, secondary or tertiary hydroxyl group in one molecule. Examples of such a hydroxyl group-containing vinyl monomer include, for example, unsaturated carboxylic acid monomers each containing a hydroxyl group, vinyl ether monomers, vinyl ketone monomers and the like. Hydroxyl group-containing unsaturated carboxylic acid monomers are preferred. Examples of the hydroxyl group-containing unsaturated carboxylic acid-based monomer include, for example, derivatives such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, esters such as maleic acid, amides and anhydrides, and preferably acrylic acid. ,
It is an ester compound such as methacrylic acid.

Examples of the hydroxyl group-containing vinyl monomer include, for example, hydroxymethyl (meth) acrylate,
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) ) Acrylate, glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, 2-chloro-3-hydroxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide , 2
-Hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide, di- (ethylene glycol) itaconate, di- (propylene glycol) itaconate, bis (2-hydroxypropyl) itaconate, bis (2-hydroxyethyl) itaconate , Bis (2-hydroxyethyl) fumarate,
Bis (2-hydroxyethyl) malate, 2-hydroxyethyl vinyl ether, hydroxymethyl vinyl ketone, allyl alcohol and the like are exemplified. Among them, hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate , Glycerol mono (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate,
Hydroxyoctyl (meth) acrylate, hydroxymethyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, 3-hydroxypropyl (meth) acrylamide and the like are preferred.

Examples of the oxy group-containing vinyl monomer include, for example, trimethoxyvinylsilane, triethoxyvinylsilane, and the like disclosed in JP-A-7-188356.
Examples include alkoxysilyl group-containing vinyl monomers such as 6-trimethoxysilyl-1,2-hexene, p-trimethoxysilylstyrene, 3-trimethoxysilylpropyl methacrylate, and 3-triethoxysilylpropyl acrylate. be able to.

The monomer having no polar group copolymerizable with both the conjugated diene monomer and the monomer copolymerizable with the conjugated diene monomer includes aromatic vinyl monomer containing no polar group. (Hereinafter, referred to as an aromatic vinyl monomer) as typical examples. Specifically, styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene,
4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene . Among them, styrene is preferred. Two or more aromatic vinyl monomers may be used in combination.

The polar group-containing diene rubber used in the present invention contains 40 to 99.99% by weight, preferably 45 to 90% by weight, more preferably 50 to 85% by weight of a conjugated diene unit.
% By weight, more preferably 55 to 80% by weight, and usually 0 to 59.99% by weight of aromatic vinyl monomer units, preferably 9.95 to 54.95% by weight, more preferably 14.
9-49.9% by weight, more preferably 19.9-4
4.9% by weight, the polar group-containing vinyl unit is usually 0.01 to
The content is 20% by weight, preferably 0.05 to 15% by weight, and more preferably 0.1 to 10% by weight. The content of each monomer unit in the polar group-containing diene rubber can be appropriately selected from the above ranges in consideration of the heat generation, abrasion resistance, strength characteristics, and the like of the tire.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the polar group-containing diene rubber is in the range of 20 to 200, preferably 30 to 150, more preferably 50 to 120. If the Mooney viscosity of the polar group-containing diene rubber is low, it is easy to manufacture, but it is difficult to obtain sufficient heat generation characteristics and abrasion resistance. The Mooney viscosity becomes too high, and the processability decreases.

(Method for producing polar group-containing diene rubber) The method for producing the polar group-containing diene rubber used in the present invention is not particularly limited, but usually an emulsion polymerization method is employed. The emulsion polymerization method is not particularly limited, and examples thereof include a method in which a monomer is emulsified and dispersed in an aqueous medium in the presence of an emulsifier and polymerized with a radical polymerization initiator.

The emulsifier used in the emulsion polymerization method is not particularly limited. However, when a carboxylic acid-based emulsifier is used, the problem of mold contamination of the copolymer obtained by high-temperature short-time crosslinking is further improved.

Examples of the carboxylic acid emulsifier include fatty acid soap and rosin acid soap. Specifically, the fatty acid soap is a long-chain aliphatic carboxylic acid having 12 to 18 carbon atoms, for example, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and the like, and a sodium salt of these mixed aliphatic carboxylic acids. Or selected from potassium salts. In addition, rosin acid soap is gum rosin,
It is selected from the sodium or potassium salts of disproportionated or hydrogenated natural rosins such as wood rosin or tall oil rosin. These natural rosins are mainly composed of abietic acid, levopimaric acid, parastolic acid, dehydroabietic acid, tetrahydroabietic acid and neoabietic acid. The amount of the emulsifier is not particularly limited, but is preferably 0.1 to 100 parts by weight of the monomer.
05 to 10 parts by weight, more preferably 0.5 to 5 parts by weight.

Examples of the radical polymerization initiator include persulfates such as ammonium persulfate and potassium persulfate;
Redox initiators such as a combination of ammonium persulfate and ferric sulfate, a combination of an organic peroxide and ferric sulfate, and a combination of hydrogen peroxide and ferric sulfate are used. The radical polymerization initiator used is not particularly limited, but usually an organic peroxide, a redox polymerization initiator system, an azo compound, a persulfate, or the like is used. The amount of the polymerization initiator to be used is usually 0.005 to 3 parts by weight per 100 parts by weight of the monomer.

The temperature of the emulsion polymerization can be appropriately selected depending on the type of the radical polymerization initiator used.
Usually, it is 0-100 ° C, preferably 0-60 ° C.
The polymerization mode may be any mode such as continuous polymerization or batch polymerization.

As the conversion of the emulsion polymerization increases, a tendency to gel is observed. Therefore, it is preferable to suppress the polymerization conversion to 90% or less, and it is particularly preferable to stop the polymerization at a conversion of 50 to 80%. The termination of the polymerization reaction is usually performed by adding a polymerization terminator to the polymerization system when a predetermined conversion is reached. Examples of the polymerization terminator include amine compounds such as diethylhydroxylamine and hydroxylamine, quinone compounds such as hydroquinone and benzoquinone, sodium nitrite,
Compounds such as sodium dithiocarbamate are used.

After termination of the emulsion polymerization reaction, unreacted monomers are removed from the obtained polymer latex, if necessary, and then, if necessary, an acid such as nitric acid or sulfuric acid is added and mixed to adjust the pH of the latex to a predetermined value. After adjusting to a value, salts such as sodium chloride, calcium chloride and potassium chloride are added and mixed as a coagulant, and the polymer is coagulated as crumb. After washing and dehydrating the crumb, dry it with a band dryer, etc.
A diene rubber can be obtained.

(Rubber Component) The rubber component used in the present invention is mainly composed of a diene rubber containing a polar group. In addition to the polar group-containing diene rubber, other rubbers may be blended as long as the effects and objects of the present invention are not impaired.

The other rubber is not particularly limited, and a diene rubber other than the polar group-containing diene rubber is usually used. Examples of such a diene rubber include natural rubber, polyisoprene rubber, emulsion-polymerized styrene-butadiene copolymer rubber, and solution-polymerized random styrene-butadiene copolymer rubber (for example, styrene unit 5 to 5).
50% by weight, 1,2-bond unit amount in butadiene unit 1
0-80%), high trans styrene-butadiene copolymer rubber (for example, 70-95% of 1,4-trans bond unit in butadiene unit), low cis polybutadiene rubber, high cis butadiene rubber, high trans butadiene Rubber (e.g., 70-95% of 1,4-trans bond unit in butadiene unit), styrene-isoprene copolymer rubber, butadiene-isoprene copolymer rubber, solution-polymerized random styrene-butadiene-isoprene copolymer rubber, Emulsion-polymerized styrene-butadiene-isoprene copolymer rubber, emulsion-polymerized styrene-acrylonitrile-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, high vinyl styrene-butadiene copolymer-
Examples thereof include low vinyl / styrene-butadiene copolymer block copolymer rubber and polystyrene-polybutadiene-polystyrene block copolymer rubber, which can be appropriately selected according to required characteristics. Among them, natural rubber, butadiene rubber, isoprene rubber, styrene-butadiene copolymer rubber, styrene-isoprene-butadiene copolymer rubber and the like are particularly preferable.

Further, rubbers other than the diene rubber include:
For example, butyl rubber, halogenated butyl rubber, ethylene-propylene-diene terpolymer rubber, epichlorohydrin rubber and the like can be used.

These rubbers can be used alone or in combination of two or more. When a polar group-containing diene rubber and another rubber are used in combination as the rubber component, the proportion of each rubber is appropriately selected according to the application and purpose. It is usually at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight.

(Reinforcing Agent) The reinforcing agent used in the present invention contains silica as an essential component, and optionally contains other reinforcing agents.

The silica is not particularly limited. For example, dry white carbon, wet white carbon, colloidal silica, and JP-A-62-262838.
And the like. Among these, wet-process white carbon containing hydrated silicic acid as a main component is particularly preferable. These silicas can be used alone or in combination of two or more.

Although the specific surface area of silica is not particularly limited, it is usually 50 to 40 in terms of nitrogen adsorption specific surface area (BET method).
0 m ² / g, preferably at 100 to 250 m ² / g, more preferably in the range of 120~190m ² / g,
Improvements such as reinforcement, abrasion resistance, and heat generation are sufficiently achieved, which is preferable. Here, the nitrogen adsorption specific surface area is AST
It is a value measured by the BET method according to MD3037-81.

The reinforcing agent other than silica is not particularly limited, but usually carbon black is used. As carbon black, for example, furnace black, acetylene black, thermal black, channel black, graphite and the like can be used. Among them, furnace black is particularly preferable, and specific examples thereof include SAF, ISAF, ISAF-HS, ISAF.
AF-LS, IISAF-HS, HAF, HAF-H
Various grades such as S, HAF-LS, FEF and the like can be mentioned. These carbon blacks can be used alone or in combination of two or more.

The nitrogen adsorption specific surface area of carbon black (N
₂ SA) is not particularly limited, but is usually 5 to 200 m ² /
g, preferably in the range of 50 to 150 m ² / g, more preferably in the range of 80 to 130 m ² / g, since the tensile strength and abrasion resistance are improved at a high level, which is suitable. The DBP adsorption amount of carbon black is not particularly limited, but is usually 5 to 300 ml / 100 g, preferably 50 to 200 ml.
ml / 100 g, more preferably 80-160 ml / 1
When it is in the range of 00 g, the tensile strength and abrasion resistance are improved at a high level, which is preferable.

As carbon black, JP-A-5-23
No. 0290, the adsorption (CTAB) specific surface area of cetyltrimethylammonium bromide is 110 to 110.
Abrasion resistance can be further improved by using a high-structure carbon black having a DBP (24 MDBP) adsorption amount of 110 to 130 ml / 100 g after repeatedly applying compression at 170 m ² / g at a pressure of 24,000 psi four times. .

The content of silica in the reinforcing agent is preferably 1
The content is 0 to 100% by weight, more preferably 30 to 100% by weight, particularly preferably 50 to 100% by weight, and further preferably 70 to 100% by weight.

(Polyether Polymer) As the polyether polymer, a polymer having an ether bond (—CO—C—) in the main chain is used without any particular limitation. As the polyether polymer, those obtained by block or random addition polymerization of oxirane compounds such as alkylene oxides, epihalohydrins, unsaturated epoxides alone or in combination of two or more are used.

Specific examples of the polyether polymer obtained by addition polymerization of an oxirane compound alone or in combination of two or more thereof include, for example, a homopolymer of alkylene oxide, a copolymer of two or more alkylene oxides, and an alkylene oxide. And a copolymer of epihalohydrin, a copolymer of an alkylene oxide and an unsaturated epoxide, a copolymer of an alkylene oxide and an epihalohydrin and an unsaturated epoxide, a homopolymer of epihalohydrin, a copolymer of two or more epihalohydrins, Examples include a copolymer of epihalohydrin and an unsaturated epoxide, a homopolymer of an unsaturated epoxide, and a copolymer of two or more unsaturated epoxides. Among them, a copolymer of two or more alkylene oxides or a copolymer of an alkylene oxide and an unsaturated epoxide is preferable, and a copolymer of an alkylene oxide and an unsaturated epoxide is particularly preferable.

Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxy-isobutane, 2,3-epoxybutane, 1,2-epoxyhexane, and 1,2-epoxyoctane. 1,2-epoxydecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane,
1,2-epoxyoctadecane, 1,2-epoxyeicosane, 1,2-epoxy-2-pentylpropane,
Examples thereof include 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, and 1,2-epoxycyclododecane. Among these, lower alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide and amylene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.

Examples of the epihalohydrin include, for example, epichlorohydrin, epibromohydrin, epiiodohydrin, 2,3-epoxy-1,1,1-trifluoropropane, 1,2-epoxy-1H, 1H, 2H, 3H,
3H-heptadecafluoroundecane and the like,
Usually, epichlorohydrin is used.

The unsaturated epoxide is not particularly limited as long as it is a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group in a molecule. For example, allyl glycidyl ether, butenyl glycidyl ether Alkenyl glycidyl ethers such as octenyl glycidyl ether; 3,4-epoxy-1
-Butene, 1,2-epoxy-5-hexene, 1,2-
Alkenyl epoxides such as epoxy-9-decene; aryl epoxides such as styrene epoxide and glycidyl phenyl ether; and the like. Among these, alkenyl glycidyl ether is preferred, and allyl glycidyl ether is particularly preferred.

Other oxirane compounds include, for example, 1,2-epoxy-1-methoxy-2-methylpropane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane And the like. These oxirane compounds can be used alone or in combination of two or more.

The type and content of the oxirane compound in the polyether polymer are appropriately selected according to the purpose of use. For example, when heat resistance and tensile strength are highly balanced, a polyether polymer (A) obtained by copolymerizing an alkylene oxide and an unsaturated epoxide is generally used. The content of the oxide is usually 85 to 99.9% by weight, preferably 90 to 99.9% by weight.
99% by weight, more preferably 95-99% by weight, and the content of unsaturated epoxide is usually 1
The range is 5 to 0.1% by weight, preferably 10 to 1% by weight, more preferably 5 to 1% by weight. In order to improve processability to a high degree, alkylene oxide is usually 50
% By weight, preferably at least 70% by weight, more preferably at least 90% by weight.
Is preferably used. Further, when an antistatic property is required in addition to heat resistance, tensile strength and workability, 50% by weight of ethylene oxide is used as the alkylene oxide.
Or more, preferably 60% by weight or more, more preferably 70% by weight.
A polyether-based polymer (C) containing not less than 10% by weight is suitably used. In order to highly balance all the properties of heat resistance, tensile strength, workability and antistatic property, ethylene oxide is usually 50 to 100% by weight as alkylene oxide in the polyether polymer (A), preferably 50 to 100% by weight. Is 60 to 99% by weight, more preferably 70 to 97% by weight.
% By weight and propylene oxide is usually 50 to 0% by weight, preferably 40 to 1% by weight, more preferably 30 to 0% by weight.
Those consisting of 3% by weight are particularly preferably used. Preferred copolymers are ethylene oxide 50-99% by weight,
It is a copolymer comprising 0 to 49% by weight of propylene oxide and 1 to 15% by weight of allyl glycidyl ether.

In order to achieve a high balance between all the properties of heat resistance, tensile strength, workability and antistatic properties, among polyether polymers, (1) ethylene oxide 50
９８98.9% by weight, preferably 60-97.5% by weight,
More preferably 70 to 96% by weight, (2) 1 to 35% by weight of propylene oxide, preferably 2 to 30% by weight, more preferably 3 to 25% by weight, and (3) 0.1 to 15% by weight of unsaturated epoxide. %, Preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, particularly preferably an ethylene oxide / propylene oxide / unsaturated epoxide terpolymer. In the terpolymer, the unsaturated epoxide is particularly preferably an alkenyl glycidyl ether such as allyl glycidyl ether.

The (co) polymer of the oxirane compound containing the terpolymer can be usually obtained by a solution polymerization method or a solvent slurry polymerization method. As a catalyst,
For example, a system in which water and acetylacetone are reacted with organoaluminum (Japanese Patent Publication No. 35-15797), a system in which triisobutylaluminum is reacted with phosphoric acid and triethylamine (Japanese Patent Publication No. 46-27534), and triisobutylaluminum are used. A system in which phosphoric acid and an organic acid salt of diazabiacycloundecene are reacted (JP-B-56-511).
No. 71); a homogeneous catalyst such as a partially hydrolyzed aluminum alkoxide and an organozinc compound (JP-B-43-2945); and a system comprising an organozinc compound and a polyhydric alcohol (JP-B-45). -7751), a system comprising a dialkyl zinc and water (JP-B-36-3).
394) and the like. When employing the solvent slurry polymerization method, a catalyst that has been pre-treated with both a monomer that provides a polymer soluble in the polymerization solution and a monomer that provides a polymer insoluble in the polymerization solvent is used. Is preferred from the viewpoint of the stability of the polymerization reaction system.

As the solvent, aromatic hydrocarbons such as toluene; pentanes such as n-pentane; hexanes such as n-hexane; alicyclic hydrocarbons such as cyclopentane; n-pentane, n-hexane,
When a solvent slurry polymerization method is employed using a solvent such as cyclopentane, for example, the catalyst is previously treated with ethylene oxide that gives a polymer insoluble in the solvent and propylene oxide that gives a polymer soluble in the solvent. As described above, it is preferable from the viewpoint of the stability of the polymerization reaction system. The treatment of the catalyst may be performed by mixing the catalyst component with a small amount of each monomer and aging at a temperature of 0 to 100 ° C, preferably 30 to 50 ° C.

In the polymerization reaction, a monomer component, a catalyst component, a polymerization solution and the like are charged into a reactor, and at a temperature of 0 to 100 ° C., preferably 30 to 70 ° C., a batch system, a semi-batch system, a continuous system, etc. Can be performed in the following manner. The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the polyether polymer is not particularly limited, but is usually 10 to 200, preferably 20 to 15.
0, more preferably in the range of 25 to 120. When the Mooney viscosity (ML _{1 + 4} , 100 ° C.) is in the range of 70 to 150, preferably 80 to 140, more preferably 85 to 120, the heat resistance, tensile strength and workability are highly balanced. It is suitable.

These polyether polymers can be used alone or in combination of two or more. The amount of the polyether polymer used is appropriately selected according to the intended use, but is usually 0.1 to 50 parts by weight, preferably 1 to 30 parts by weight, based on 100 parts by weight of the diene rubber.
Parts by weight, more preferably 3 to 15 parts by weight.
If the amount of the polyether polymer is excessively small, the effect of improving heat resistance, tensile strength and workability is not sufficient, and conversely, if the amount is excessively large, the heat generation is not sufficient, and both are preferable. Absent.

The silane coupling agent is not particularly restricted but includes, for example, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxy-ethoxy) silane and β- (3,4-epoxycyclohexyl) -ethyltriethylsilane. Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, N-β (aminoethyl) -γ-
Aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane,
N-phenyl-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, bis (3- (triethoxysilyl) propyl) tetrasulfide, And JP-A-6-2
And tetrasulfides such as γ-trimethoxysilylpropyldimethylthiocarbamyltetrasulfide and γ-trimethoxysilylpropylbenzothiazyltetrasulfide described in JP-A-48116.

(Silylation Agent) In the present invention, the silyl agent added to change the silica surface to hydrophobic is described in JP-A-5-51484, JP-A-7-164810, and JP-A-7-165959. Gazette, JP-A-8-25
This is known in, for example, JP-A-9738 and JP-A-8-337688. Specifically, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, triphenylmethoxysilane, p
-Methylphenyltrimethoxysilane, p-methylphenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane,
3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-nitrylpropyltrimethoxysilane, 3-
Nitrilepropyltriethoxysilane, p-bromophenyltrimethoxysilane, p-bromophenyltriethoxysilane, toluyltrimethoxysilane, toluyltriethoxysilane, propyltrimethoxysilane chloride,
Examples thereof include propyltriethoxysilane chloride, 1,1-difluoropropyltrimethoxysilane, 1,1-difluoropropyltriethoxysilane, cyanopropyltrimethoxysilane, and cyanopropyltriethoxysilane. The silylating agent used in the present invention preferably has a structure represented by the following general formula 1. General formula:

Embedded image Wherein R is an alkyl group, A is a phenyl or alkylphenyl group, B is a phenyl, alkylphenyl or alkoxy group, and C is a phenyl, alkylphenyl or alkoxy group. Examples of the silylating agent include phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane, diphenyldimethoxysilane, triphenylethoxysilane, and triphenylmethoxysilane. Particularly, phenyltriethoxysilane is preferable.

(Rubber Composition) The rubber composition of the present invention comprises (a) a rubber component containing a diene rubber as a main component, (b) a reinforcing agent containing silica, (c) a polyether polymer,
It contains (d) a silane coupling agent and (e) a silylating agent.

The amount of the reinforcing agent containing silica (b) to be used is preferably 10 to 200 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 30 to 100 parts by weight of the rubber component (a). １２０120 parts by weight. If it is too large, dispersion may not be successful. If too little,
The reinforcing effect is small and may not meet the purpose.

The amount of the (c) polyether polymer is determined according to the intended use, but is preferably 0.1 to 50 parts by weight, more preferably 1 to 50 parts by weight, per 100 parts by weight of the rubber component (a). 30 parts by weight, particularly preferably 3 to 15 parts by weight. If the polyether polymer is too small, heat resistance,
Tensile strength, workability, etc. may be insufficient, and too much may result in insufficient heat generation.

(D) The amount of the silane coupling agent is also determined according to the application, but is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 20 parts by weight, per 100 parts by weight of silica.
It is 15 parts by weight, particularly preferably 1 to 10 parts by weight. If the amount is too large, the effect is not sufficient with respect to the added amount, and the strength and the like may be adversely affected. If the amount is too small, the effect is not sufficiently exhibited.

(E) The amount of the silylating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of rubber. It is. If the amount of the silylating agent is too large, the hardness of the rubber composition may be reduced or may be deposited on the surface to reduce the slip resistance of the rubber composition. If the amount of the silylating agent is too small, the effect may not be sufficiently exhibited.

(Other Compounds) In addition to the above components, other additives such as stabilizers, cross-linking agents, cross-linking accelerators, cross-linking activators, anti-aging agents, activators, plasticizers, lubricants, and fillers are used in accordance with the conventional methods. Can be contained in necessary amounts.

The stabilizer used in the present invention is not particularly limited, and examples thereof include a phenol stabilizer, a sulfur stabilizer and a phosphorus stabilizer.

The phenolic stabilizers used in the present invention are those known in JP-A-4-252243. Examples of the phenolic stabilizer include, for example, 2,6-
Di-tert-butyl-4-methylphenol, 2,6
-Di-tert-butyl-4-ethylphenol, 2,
6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-iso-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,4,6-triphenyl Cyclohexylphenol, 2,6-di-tert-butyl-4-methoxyphenol, 2,6-di-phenol-4-octadecyloxyphenol, n-octadecyl-3- (3 ′,
5'-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3-
(3 ', 5'-di-tert-butyl-4'-hydroxy-phenyl) propionate] -methane, 1,3,5
-Trimethyl-2,4,6-tris (3,5-di-te
In addition to common phenolic stabilizers such as rt-butyl-4-hydroxybenzyl) benzene, sulfur-containing phenolic stabilizers are exemplified.

Examples of the sulfur-containing phenolic stabilizer include:
For example, 2,4-bis (octylthiomethyl) -6-methylphenol, 2,4-bis (2 ', 3'-di-hydroxypropylthiomethyl) -3,6-di-methylphenol, 2,4 -Bis (2'-acetyloxyethylthiomethyl) -3,6-di-methylphenol and the like.

The phosphorus stabilizers used in the present invention are also known, for example, tris (nonylphenyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), tris (2,4-di-phosphite). t
tert-butylphenyl) phosphite and the like.

A sulfur-based stabilizer may be added. Examples of such a sulfur-based stabilizer include, for example, pentaerythritol-tetrakis- (β-lauryl-thio-propionate), dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate. ,
Distearyl-3,3'-thiodipropionate and the like are illustrated.

The crosslinking agent is not particularly limited. For example, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur,
Sulfur such as highly dispersible sulfur; sulfur halides such as sulfur monochloride and sulfur dichloride; organic peroxides such as dicumyl peroxide and ditert-butyl peroxide; p-quinone dioxime, p, p'-di Quinone dioximes such as benzoylquinone dioxime; organic polyamine compounds such as triethylenetetramine, hexamethylenediaminecarbamate and 4,4'-methylenebis-o-chloroaniline; alkylphenol resins having a methylol group; . Among these, sulfur is preferred, and powdered sulfur is particularly preferred. These crosslinking agents are used alone or in combination of two or more.

The mixing ratio of the crosslinking agent is as follows: (a) rubber component 10
Usually, 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 0 parts by weight.
It is in the range of parts by weight. When the compounding ratio of the cross-linking agent is within this range, it is particularly preferable because it has excellent properties such as heat resistance and residual strain as well as excellent tensile strength and wear resistance.

Examples of the crosslinking accelerator include N-cyclohexyl-2-benzothiazolesulfenamide and N-cyclohexyl-2-benzothiazolesulfenamide.
-T-butyl-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N-oxyethylene-2-benzothiazolesulfenamide, N, N'-diisopropyl-2-
Sulfenamide-based cross-linking accelerators such as benzothiazole sulfenamide; guanidine-based cross-linking accelerators such as diphenylguanidine, diortitolylguanidine, ortho-tolylbiguanidine; thiocarbanilide, dioltotolylthiourea, ethylenethiourea, diethylthiourea, Thiourea-based crosslinking accelerators such as trimethylthiourea; 2-mercaptobenzothiazole, dibenzothiazyl disulfide, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole sodium salt;
Thiazole crosslinking accelerators such as 2-mercaptobenzothiazolecyclohexylamine salt and 2- (2,4-dinitrophenylthio) benzothiazole; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, Thiuram-based crosslinking accelerators such as dipentamethylenethiuram tetrasulfide; sodium dimethyldithiocarbamate, sodium diethyldithiocarbamate, sodium di-n-butyldithiocarbamate, lead dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc n-butyldithiocarbamate, zinc pentamethylenedithiocarbamate, ethylphenyldithiocarbamate Acceleration of dithiocarbamic acid crosslinking such as tellurium diethyldithiocarbamate, selenium dimethyldithiocarbamate, selenium diethyldithiocarbamate, copper dimethyldithiocarbamate, iron dimethyldithiocarbamate, diethylamine diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, and pipecoline methylpentamethylenedithiocarbamate. Crosslinking promoters such as sodium isopropyl xanthogenate, zinc isopropyl xanthogenate, and zinc butyl xanthogenate; and the like.

Each of these crosslinking accelerators may be
Alternatively, two or more of them are used in combination, but those containing at least a sulfenamide-based crosslinking accelerator are particularly preferred. Among those containing a sulfenamide-based cross-linking accelerator, the proportion of the sulfenamide-based cross-linking accelerator is preferably 30% by weight or more of all the cross-linking accelerators, more preferably 50% by weight or more, and 70% by weight. % Or more is particularly preferable. The mixing ratio of the crosslinking accelerator is 100
The amount is usually 0.1 to 15 parts by weight, preferably 0.3 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight with respect to parts by weight.

The crosslinking activator is not particularly limited. For example, higher fatty acids such as stearic acid and zinc oxide can be used. As zinc oxide, for example,
It is preferable to use one having a high surface activity and a particle size of 5 μm or less.
Active zinc white of 5 to 0.2 μm and zinc white of 0.3 to 1 μm can be exemplified. As the zinc oxide, a zinc oxide surface-treated with an amine-based dispersant or wetting agent can be used.

These crosslinking activators can be used alone or in combination of two or more. The mixing ratio of the crosslinking activator is appropriately selected depending on the type of the crosslinking activator. When higher fatty acids are used, solid rubber content 1
Usually, 0.05 to 15 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight with respect to 00 parts by weight.
Mix by weight. When zinc oxide is used, it is usually 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 2 parts by weight per 100 parts by weight of the solid rubber.
Mix by weight. When the compounding ratio of zinc oxide is in this range, properties such as workability, tensile strength and wear resistance are highly balanced and suitable.

Examples of other compounding agents include coupling agents other than silane coupling agents; activators such as diethylene glycol, polyethylene glycol and silicone oil; fillers such as calcium carbonate, talc and clay; process oils and waxes Is mentioned.

The rubber composition of the present invention can be obtained by compounding each component according to a conventional method. For example, each component is added to and dispersed in an organic solvent liquid in which (a) a rubber component dissolved or dispersed in an organic solvent is dissolved or dispersed,
The organic solvent may be removed by a steam stripping method or a method using a hot roll, or may be kneaded using a roll, a Banbury, or an extruder.

(Use) The rubber composition of the present invention can be used for various parts of a tire such as a tread, a carcass, a sidewall, a bead, or a hose, a window frame, a belt, or the like.
Use for rubber products such as shoe soles, anti-vibration rubber, automobile parts,
Further, it can be used as a resin-reinforced rubber such as impact-resistant polystyrene and ABS resin. In particular, the rubber composition of the present invention makes use of the above characteristics, and is particularly excellent in tire tread of fuel-efficient tires, but also in all season tires, high performance tires, tire treads such as studless tires, side walls, and under treads. , Carcass, beat part, etc.

[0084]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Production Examples, Examples and Comparative Examples. Various physical properties were measured according to the following methods. (1) The styrene unit amount in the diene rubber is determined according to JIS K
It was measured according to 6383 (refractive index method). (2) The amino group-containing monomer unit amount in the diene rubber is as follows:
The copolymer was dissolved in tetrahydrofuran, reprecipitated and coagulated twice with methanol / acetone (50/50% by volume), dried under vacuum, and measured by 500 MHz 1H-NMR. (3) The amount of the hydroxyl-containing monomer unit in the diene rubber is determined according to the method described in JP-A-3-174408.
After treating the polymer with phenyl isocyanate, ¹³ C-N
It was calculated by quantifying the phenyl group of phenyl isocyanate in the MR spectrum.

(4) Mooney viscosity (ML)_{1 + 4}, 100
° C) was measured according to JIS K6300. (5) The monomer unit amount of the polyether polymer is as follows: 1H-
Measured by NMR analysis. (6) Mooney scorch time (t5) is based on
In accordance with SRIS 3102, an unvulcanized rubber composition
And 160 by the oscillating rheometer.
The scorch time in ° C. was measured. Examples 1 to 5 and
For Comparative Examples 2 to 4, Mooney Squaw of Comparative Example 1 was used.
Examples 6 to 10 are indices with the time h (t5) being 100.
Is the Mooney scorch time of Comparative Example 5 (t5)
Is shown as an index with 100 as the index.

(7) The vulcanization rate △ (t90-t10) is based on SRIS3102 of the Japan Rubber Association, and the time required for an unvulcanized rubber composition to reach 90% of the maximum torque at 160 ° C. by an oscillating rheometer ( t90) and time to reach 5% of the maximum torque (t10)
(T90-t10) was measured. For Examples 1 to 5 and Comparative Examples 2 to 4, the vulcanization rate 比較 (t
Examples 6 to 10 were calculated using an index of 90-t10) as 100.
Is shown as an index with the vulcanization rate 比較 (t90-t10) of Comparative Example 5 being 100. (8) The heat generation index is RDA-II manufactured by Rheometrics.
The tan δ at 1% torsion, 20 Hz, and 60 ° C. was measured using Examples, and the index of Comparative Examples 1 to 5 was used for Examples 1 to 5 and Comparative Examples 2 to 4, and Comparative Example 5 was used for Examples 6 to 10. Is shown as an index with 100 as the index.

Reference Examples 1-3 In a tank equipped with a stirrer, 200 parts of water, 3 parts of rosin acid soap, t
0.15 parts of dodecyl mercaptan and a monomer having the composition shown in Table 1 were charged. The reactor temperature was set to 5 ° C, and cumene hydroperoxide 0.1 as a radical polymerization initiator was used.
Parts, sodium-formaldehyde-sulfoxylate (0.2 part) and ferric sulfate (0.01 part) were added to initiate polymerization. When the conversion reached 70%, the reaction was stopped by adding diethylhydroxylamine. Next, the unreacted monomer is recovered, and naphthenic oil (Diana Process Oil NS-24, manufactured by Idemitsu Kosan Co., Ltd., aroma content: 5% by weight)
Was mixed with 37.5 parts by weight per 100 parts by weight of the polymer.
This was coagulated with sulfuric acid and salt to form crumbs, and dried with a crumb dryer to obtain diene rubbers 1 to 3.
Table 1 shows the properties of the diene polymer. Diene rubber 1,
Reference numeral 2 denotes a diene rubber containing a polar group.

[0088]

[Table 1]

Reference Example 4 An autoclave with a stirrer having an internal volume of 3 liters was replaced with nitrogen, and 1170 g of toluene, 158.7 g of triisobutylaluminum, and 296.4 of diethyl ether were used.
g. The internal temperature was set at 30 ° C., and 23.5 g of orthophosphoric acid was gradually added with stirring. Further, 12.1 g of triethylamine was added, and an aging reaction was performed at 60 ° C. for 2 hours to obtain a catalyst solution.

An autoclave having an internal volume of 5 liters equipped with a stirrer was replaced with nitrogen, and 2100 g of n-hexane and 63 g of a catalyst solution were charged. With the internal temperature set at 30 ° C., 5% of a mixed solution consisting of 240 g of ethylene oxide, 60 g of propylene oxide and 300 g of n-hexane was added with stirring. After reacting for 1 hour, the internal temperature was raised to 60
C., and the remaining 95% of the mixed solution was continuously added over 5 hours. After completion of the addition, a post-reaction was performed for 2 hours. The polymerization reaction rate was 99%. The polymer was separated and collected by a centrifugal separator, and vacuum dried at 60 ° C. overnight. Table 2 shows the properties of the obtained polyether polymer 1.

Reference Example 5 240 g of ethylene oxide, propylene oxide 6
0 g and 300 g of n-hexane were mixed with 261 g of ethylene oxide and 30 g of propylene oxide.
g, allyl glycidyl ether 9 g, n-hexane 30
The same procedure as in Reference Example 4 was carried out except for using 0 g of the mixed solvent, to obtain a polyether polymer 2. Table 2 shows the properties of the polyether polymer 2.

[0092]

[Table 2]

Examples 1 to 10 and Comparative Examples 1 to 5 Based on the formulation of Table 3 (Examples 1 to 5 and Comparative Examples 1 to 4) and Table 4 (Examples 6 to 10 and Comparative Example 5) Capacity 2
In a 50 ml Brabender type mixer, the whole amount of the raw rubber, half the amount of silica and half the amount of the silane coupling agent were mixed at 170 ° C. for 2 minutes, and the remaining compounding agents except for sulfur and the crosslinking accelerator were added. For 2 minutes. The obtained mixture, sulfur and a crosslinking accelerator were added to an open roll at 50 ° C. and kneaded, and then press-crosslinked at 160 ° C. for 30 minutes to prepare a test piece, and each physical property was measured. The results are shown in Tables 3 and 4.

[0094]

[Table 3]

[0095]

[Table 4]

Silica was Z1165MP (manufactured by Rhone Poulin, nitrogen adsorption specific surface area: 175 m ² / g), silylating agent 1 was phenyltriethoxysilane, silylating agent 2
Is diphenyldiethoxysilane, silane coupling agent 1 is Si69 (manufactured by Degussa), silane coupling agent 2 is γ-mercaptopropyltrimethoxysilane, zinc oxide is zinc white # 1 (manufactured by Honjo Chemical Co., particle size 0.4 μm).
m), the oil used was Sansen 410 (manufactured by Nippon Oil Co., Ltd.), the antioxidant used was Nocrack 6C (manufactured by Ouchi Shinkosha), and the crosslinking accelerator used was Noxeller CZ (manufactured by Ouchi Shinkosha). BR1220 (manufactured by Zeon Corporation) was used for butadiene rubber, and RSS # 3 was used for natural rubber.

[0097]

The rubber composition of the present invention has excellent strength characteristics because silica is sufficiently dispersed, and also has excellent fuel efficiency and high crosslinking speed because silica is used as a reinforcing agent. , Scorch is less likely to occur. It can significantly improve the tensile strength, heat build-up, and abrasion resistance, which were disadvantages without impairing the rolling resistance, which is a feature of the silica-containing material, and has excellent workability.

(Preferred embodiment) According to the present invention, (a)
A rubber component mainly comprising a polar group-containing diene rubber,
Preferred embodiments of the diene rubber composition containing (b) a reinforcing agent containing silica, (c) a polyether polymer, (d) a silane coupling agent and (e) a silylating agent are summarized below. It is as follows.

(1) The polar group-containing diene rubber is (i)
The conjugated diene unit is usually 40 to 99.99% by weight, preferably 45 to 90% by weight, more preferably 50 to 85% by weight, still more preferably 55 to 80% by weight, and (ii) the polar unit-containing vinyl unit is usually 0%. 0.01 to 20% by weight, preferably 0.05 to 15% by weight, more preferably 0.1 to 1% by weight.
0% by weight, and (iii) above (i) and (ii)
A monomer unit containing no polar group copolymerizable with the monomer component of the present invention, preferably an aromatic vinyl monomer unit, usually from 0 to 5
9.99% by weight, preferably 9.95 to 54.95% by weight, more preferably 14.9 to 49.9% by weight, and still more preferably 19.9 to 44.9% by weight. (2) The polar group-containing vinyl unit of the above item (1) is a unit of a vinyl monomer containing at least one polar group having a hetero atom.

(3) The polar group-containing vinyl monomer having a hetero atom of the above item (2) is an amino group-containing vinyl monomer,
It is selected from a hydroxyl group-containing vinyl monomer and an oxy group-containing vinyl monomer, is preferably selected from a hydroxyl group-containing vinyl monomer and an amino group-containing vinyl monomer, and is more preferably an amino group-containing vinyl monomer. It is a vinyl monomer, most preferably a tertiary amino group-containing vinyl monomer. (4) Mooney viscosity (ML) of polar group-containing diene rubber
_{1 + 4} , 100 ° C) is 20 to 200, preferably 30 to 200.
150, more preferably in the range of 50 to 120. (5) The content of silica in the reinforcing agent is preferably from 10 to
100% by weight, more preferably 30 to 100% by weight, particularly preferably 50 to 100% by weight, even more preferably 7 to 100% by weight.
0 to 100% by weight.

(6) Silica is selected from dry-process white carbon, wet-process white carbon, colloidal silica, and precipitated silica, particularly preferably wet-process white carbon containing hydrous silicic acid as a main component. The specific surface area is the nitrogen adsorption specific surface area (BET method).
And usually 50 to 400 m ² / g, preferably 100 to ²
50 m ² / g, more preferably 120~190m ² /
g. (7) The amount of the reinforcing agent containing silica is 100
10 to 200 parts by weight, more preferably 20 to 150 parts by weight, particularly preferably 30 to 100 parts by weight with respect to parts by weight.
120 parts by weight. (8) The polyether polymer is an alkylene oxide,
A silane compound selected from epihalohydrin and unsaturated epoxide, alone or in combination of two or more, is subjected to block or random addition polymerization.

(9) The amount of the polyether polymer is preferably 0.1 to 50 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 3 to 15 parts by weight, based on 100 parts by weight of the rubber component. Department. (10) The amount of the silane coupling agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight with respect to 100 parts by weight of silica.
Parts by weight. (11) The amount of the silylating agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 15 parts by weight, and particularly preferably 1 to 10 parts by weight based on 100 parts by weight of the rubber.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08K 3:36 5:54)

Claims (1)

[Claims] 1. A rubber component containing (a) a polar group-containing diene rubber as a main component, (b) a reinforcing agent containing silica,
A diene rubber composition containing (c) a polyether polymer, (d) a silane coupling agent, and (e) a silylating agent.