JP5019752B2 - Modified natural rubber and method for producing the same, rubber composition and tire - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a modified natural rubber, a method for producing the same, and a rubber composition and a tire using the modified natural rubber, and more particularly to a modified natural rubber capable of imparting excellent wear resistance to a tire when used in a tread. It is about rubber.

  In recent years, there is an increasing demand for lower fuel consumption of automobiles, and tires with low rolling resistance are required. Therefore, a rubber composition excellent in low loss (low heat generation) is required as a rubber composition used for tire treads and the like. In addition, a rubber composition for a tread is required to have excellent wear resistance and fracture characteristics in addition to low loss. In order to improve the low loss, wear resistance and fracture characteristics of a rubber composition in which a filler such as carbon black or silica is blended with the rubber component in response to these requirements, the filler and rubber in the rubber composition are improved. It is effective to improve the affinity with the components.

  On the other hand, natural rubber is used in a large amount by taking advantage of its excellent physical properties. For example, a technique for graft polymerization by adding a vinyl monomer to natural rubber latex is known (Patent Documents 1 to 4). reference). Although the grafted natural rubber obtained by this technique has been put to practical use for adhesives and the like, the grafted natural rubber is used in a large amount (20 to 50 mass) as a monomer in order to change the properties of the natural rubber itself. %) Vinyl compound is grafted, and when blended with a filler, the viscosity is greatly increased and the processability is lowered. In addition, since a large amount of vinyl compound is introduced into the natural rubber molecular chain, the excellent physical properties of natural rubber (stress-strain curve in viscoelasticity, tensile test, etc.) are impaired.

  Therefore, by using a small amount of a polar group-containing monomer as the vinyl monomer, the compatibility with the filler is improved while maintaining the original physical properties of natural rubber without lowering the processability. The reinforcing effect by the agent can be improved (see Patent Document 5). The rubber composition using the modified natural rubber obtained by this technique can improve the low loss property and the wear resistance due to the above effects.

JP-A-5-287121 JP-A-6-329702 Japanese Patent Laid-Open No. 9-25468 JP 2002-138266 A International Publication No. 2004/106397 Pamphlet

  However, the improvement of the filler reinforcing effect by the modified natural rubber alone cannot sufficiently satisfy the demand for improvement in wear resistance, which is becoming more severe year by year, and there is still room for improvement in the wear resistance of the rubber composition. There is.

  Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art and to use the modified natural rubber capable of further improving the wear resistance of the rubber composition by using it as a rubber component of the rubber composition, and the rubber It is in providing the manufacturing method of a composition. Another object of the present invention is to provide a rubber composition using the modified natural rubber and a tire using the rubber composition.

  As a result of intensive investigations to achieve the above object, the present inventors grafted a polar group-containing monomer to natural rubber molecules in natural rubber latex, further solidified and dried, and then subjected to mechanical shearing force. Thus, it was found that a modified natural rubber capable of further improving the wear resistance of the rubber composition was obtained, and the present invention was completed.

That is, the modified natural rubber of the present invention is obtained by adding a polar group-containing monomer to natural rubber latex, graft polymerizing the polar group-containing monomer to natural rubber molecules in the natural rubber latex, and further coagulating and drying. Later obtained by applying mechanical shear force ,
The means for applying the mechanical shear force is at least one of a closed twin-screw kneader, a dry prebreaker, and a twin-screw extruder.
The polar group of the polar group-containing monomer is amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, It is at least one selected from the group consisting of oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group. To do.

  In the modified natural rubber of the present invention, the graft amount of the polar group-containing monomer is preferably 0.01 to 5.0% by mass with respect to the rubber component of the natural rubber latex.

The method for producing a modified natural rubber according to the present invention comprises adding a polar group-containing monomer to natural rubber latex, graft-polymerizing the polar group-containing monomer to natural rubber molecules in the natural rubber latex, and further coagulating. And after drying, the mechanical shearing force is applied , and the means for applying the mechanical shearing force is at least one of a closed twin-screw kneader, a dry prebreaker, and a twin-screw extruder, and the polar group-containing single unit. The polar group of the monomer is amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, oxycarbonyl group, sulfide Group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group. Characterized in that it is at least one selected from the group.

  Furthermore, the rubber composition of the present invention is characterized by using the modified natural rubber, and the tire of the present invention is characterized by using the rubber composition for a tire member, particularly a tread.

  According to the present invention, the rubber composition in the natural rubber latex is subjected to graft polymerization with a polar group-containing monomer, further solidified and dried, and then subjected to mechanical shearing force to thereby improve the wear resistance of the rubber composition. A modified natural rubber that can be further improved and a method for producing the modified natural rubber can be provided. Moreover, the rubber composition and tire excellent in abrasion resistance using this modified natural rubber can be provided.

  The present invention is described in detail below. The modified natural rubber of the present invention is obtained by adding a polar group-containing monomer to natural rubber latex, graft-polymerizing the polar group-containing monomer to natural rubber molecules in the natural rubber latex, and further coagulating and drying. It is obtained by applying a mechanical shearing force. The modified natural rubber in which the polar group-containing monomer is introduced into the natural rubber molecule by graft polymerization has a higher affinity for fillers such as carbon black and silica than unmodified natural rubber. Therefore, the rubber composition using the modified natural rubber as a rubber component has high dispersibility of the filler with respect to the rubber component, and the reinforcing effect of the filler is sufficiently exerted to greatly improve the low loss property. . In this case, although the abrasion resistance of the rubber composition is improved, it is not sufficient. This is considered that gel is formed in the process of introducing the polar group-containing monomer into the natural rubber molecule by graft polymerization, and the wear resistance is lowered. As a result of investigations by the present inventors, it has been found that the gel content can be reduced and the wear resistance of the rubber composition can be improved by applying a mechanical shearing force to the modified natural rubber.

  The natural rubber latex used for the production of the modified natural rubber is not particularly limited. For example, field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant or an enzyme, and a combination thereof. A thing etc. can be used.

  The polar group-containing monomer added to the natural rubber latex is not particularly limited as long as it has at least one polar group in the molecule and can be graft-polymerized with the natural rubber molecule. Here, the polar group-containing monomer preferably has a carbon-carbon double bond in the molecule for graft polymerization with a natural rubber molecule, and is preferably a polar group-containing vinyl monomer. .

  As means for giving a mechanical shearing force after graft polymerization of a polar group-containing monomer on the natural rubber molecule in the natural rubber latex and further coagulation and drying, a plastmill, a kneader, a dry prebreaker, and a biaxial An extrusion device is effective.

  Specific examples of the polar group of the polar group-containing monomer include amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl Preferred examples include a group, an epoxy group, an oxycarbonyl group, a sulfide group, a disulfide group, a sulfonyl group, a sulfinyl group, a thiocarbonyl group, a nitrogen-containing heterocyclic group, an oxygen-containing heterocyclic group, and an alkoxysilyl group. These monomers containing polar groups may be used alone or in combination of two or more.

  Examples of the monomer containing an amino group include polymerizable monomers containing at least one amino group selected from primary, secondary and tertiary amino groups in one molecule. Among the polymerizable monomers having an amino group, a tertiary amino group-containing monomer such as dialkylaminoalkyl (meth) acrylate is particularly preferable. These amino group-containing monomers may be used alone or in a combination of two or more.

  Here, as the primary amino group-containing monomer, acrylamide, methacrylamide, 4-vinylaniline, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, aminobutyl (meth) ) Acrylate and the like.

  The secondary amino group-containing monomer includes (1) anilinostyrene, β-phenyl-p-anilinostyrene, β-cyano-p-anilinostyrene, β-cyano-β-methyl-p. -Anilinostyrene, β-chloro-p-anilinostyrene, β-carboxy-p-anilinostyrene, β-methoxycarbonyl-p-anilinostyrene, β- (2-hydroxyethoxy) carbonyl-p-anilino Anilinostyrenes such as styrene, β-formyl-p-anilinostyrene, β-formyl-β-methyl-p-anilinostyrene, α-carboxy-β-carboxy-β-phenyl-p-anilinostyrene, (2) 1-anilinophenyl-1,3-butadiene, 1-anilinophenyl-3-methyl-1,3-butadiene, 1-anilinophenyl-3-chloro-1,3-butadiene, 3-aniline Linophenyl-2-methyl-1,3-butadiene, 1-anilinov Nyl-2-chloro-1,3-butadiene, 2-anilinophenyl-1,3-butadiene, 2-anilinophenyl-3-methyl-1,3-butadiene, 2-anilinophenyl-3-chloro- Anilinophenylbutadienes such as 1,3-butadiene, (3) N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methylolacrylamide, N- (4-anilinophenyl) methacrylamide, etc. N-mono substituted (meth) acrylamides and the like can be mentioned.

  Furthermore, examples of the tertiary amino group-containing monomer include N, N-disubstituted aminoalkyl (meth) acrylate and N, N-disubstituted aminoalkyl (meth) acrylamide.

  Examples of the N, N-disubstituted aminoalkyl (meth) acrylate include N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, 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, N-dioctyl Aminoethyl (meth) acrylate, esters of acrylic acid or methacrylic acid such as acryloyl morpholine and the like. Among these, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dipropylaminoethyl (meth) acrylate, N, N-dioctylaminoethyl (meth) Particularly preferred are acrylate, N-methyl-N-ethylaminoethyl (meth) acrylate, and the like.

  Examples of the N, N-disubstituted aminoalkyl (meth) acrylamide 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 ( Data) acrylamide, N, N-dihexyl-aminopropyl (meth) acrylamide, N, N-acrylamide compounds such as dioctyl aminopropyl (meth) acrylamide or methacrylamide compounds and the like. Among these, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminopropyl (meth) acrylamide, N, N-dioctylaminopropyl (meth) acrylamide and the like are particularly preferable.

  Examples of the nitrile group-containing monomer include (meth) acrylonitrile, vinylidene cyanide, and the like. These nitrile group-containing monomers may be used alone or in a combination of two or more.

  Examples of the monomer containing a hydroxyl group include polymerizable monomers having at least one primary, secondary, and tertiary hydroxyl group in one molecule. Examples of such monomers include hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyl group-containing vinyl ether monomers, hydroxyl group-containing vinyl ketone monomers, and the like. Here, specific examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyalkylene glycols such as polyethylene glycol and polypropylene glycol (the number of alkylene glycol units is, for example, 2 to 23 Mono (meth) acrylates; N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, etc. Hydroxyl group-containing unsaturated amides; o-hydroxy Hydroxyl group-containing vinyl such as tylene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl alcohol Aromatic compounds etc. are mentioned. Among these, hydroxyl group-containing unsaturated carboxylic acid monomers, hydroxyalkyl (meth) acrylates, and hydroxyl group-containing vinyl aromatic compounds are preferable, and hydroxyl group-containing unsaturated carboxylic acid monomers are particularly preferable. Here, examples of the hydroxyl group-containing unsaturated carboxylic acid-based monomer include esters such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, amides, and anhydrides. Among these, Particularly preferred are esters such as acrylic acid and methacrylic acid. These hydroxyl group-containing monomers may be used alone or in a combination of two or more.

  Examples of the monomer containing a carboxyl group include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, cinnamic acid; non-phthalic acid, succinic acid, adipic acid Examples thereof include free carboxyl group-containing esters such as monoesters of a polymerizable polycarboxylic acid and a hydroxyl group-containing unsaturated compound such as (meth) allyl alcohol and 2-hydroxyethyl (meth) acrylate, and salts thereof. Of these, unsaturated carboxylic acids are particularly preferred. These carboxyl group-containing monomers may be used alone or in a combination of two or more.

  Examples of the monomer containing an epoxy group include (meth) allyl glycidyl ether, glycidyl (meth) acrylate, and 3,4-oxycyclohexyl (meth) acrylate. These epoxy group-containing monomers may be used alone or in combination of two or more.

  In the monomer containing the nitrogen-containing heterocyclic group, the nitrogen-containing heterocyclic ring includes pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, pyrazine, indole, quinoline, purine, phenazine, pteridine, Examples include melamine. The nitrogen-containing heterocycle may contain other heteroatoms in the ring. Here, as a monomer containing a pyridyl group as a nitrogen-containing heterocyclic group, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 5-methyl-2-vinylpyridine, 5-ethyl-2- Examples include vinyl compounds containing a pyridyl group such as vinyl pyridine, among which 2-vinyl pyridine, 4-vinyl pyridine and the like are particularly preferable. These nitrogen-containing heterocyclic group-containing monomers may be used alone or in a combination of two or more.

  Examples of the monomer containing the alkoxysilyl group include (meth) acryloxymethyltrimethoxysilane, (meth) acryloxymethylmethyldimethoxysilane, (meth) acryloxymethyldimethylmethoxysilane, (meth) acryloxymethyltrimethoxysilane. Ethoxysilane, (meth) acryloxymethylmethyldiethoxysilane, (meth) acryloxymethyldimethylethoxysilane, (meth) acryloxymethyltripropoxysilane, (meth) acryloxymethylmethyldipropoxysilane, (meth) acryloxy Methyldimethylpropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyltri Ethoxysilane, γ -(Meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ -(Meth) acryloxypropyldimethylpropoxysilane, γ- (meth) acryloxypropylmethyldiphenoxysilane, γ- (meth) acryloxypropyldimethylphenoxysilane, γ- (meth) acryloxypropylmethyldibenzyloxysilane, γ- (meth) acryloxypropyldimethylbenzyloxysilane, trimethoxyvinylsilane, triethoxyvinylsilane, 6-trimethoxysilyl-1,2-hexene, p-trimethoxysilylstyrene and the like can be mentioned. These alkoxysilyl group-containing monomers may be used alone or in a combination of two or more.

  In the present invention, the graft polymerization of the polar group-containing monomer to the natural rubber molecule is carried out by emulsion polymerization. Here, in the emulsion polymerization, generally, the polar group-containing monomer is added to a solution obtained by adding water and, if necessary, an emulsifier to a natural rubber latex, and a polymerization initiator is further added. It is preferable to polymerize the polar group-containing monomer by stirring at the temperature. In addition, in the addition of the polar group-containing monomer to the natural rubber latex, an emulsifier may be added to the natural rubber latex in advance, or after emulsifying the polar group-containing monomer with the emulsifier, May be added. In addition, it does not specifically limit as an emulsifier which can be used for emulsification of a natural rubber latex and / or a polar group containing monomer, Nonionic surfactants, such as polyoxyethylene lauryl ether, are mentioned.

  There is no restriction | limiting in particular as said polymerization initiator, The polymerization initiator for various emulsion polymerization can be used, and there is no restriction | limiting in particular also about the addition method. Examples of commonly used polymerization initiators include benzoyl peroxide, hydrogen peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 2,2-azobisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2-diaminopropane) dihydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), potassium persulfate, sodium persulfate And ammonium persulfate. In order to lower the polymerization temperature, it is preferable to use a redox polymerization initiator. Examples of the reducing agent to be combined with the peroxide in the redox polymerization initiator include tetraethylenepentamine, mercaptans, acidic sodium sulfite, reducing metal ions, ascorbic acid and the like. A preferred combination of a peroxide and a reducing agent in the redox polymerization initiator includes a combination of tert-butyl hydroperoxide and tetraethylenepentamine.

  In order to improve the low loss and wear resistance without lowering the processability of the rubber composition by adding a filler such as carbon black or silica to the modified natural rubber, the polar group is added to each natural rubber molecule. Since it is important that the contained monomer is introduced in a small amount and uniformly, the addition amount of the polymerization initiator is preferably in the range of 1 to 100 mol%, preferably 10 to 100 mol% with respect to the polar group-containing monomer. The range of is more preferable.

  Each component described above is charged into a reaction vessel and reacted at 30 to 80 ° C. for 10 minutes to 7 hours, whereby a modified natural rubber latex in which the polar group-containing monomer is graft-polymerized to a natural rubber molecule is obtained. Furthermore, the modified natural rubber latex is coagulated, washed, and then dried using a dryer such as a vacuum dryer, air dryer, drum dryer or the like to obtain a modified natural rubber. Here, the coagulant used for coagulating the modified natural rubber latex is not particularly limited, and examples thereof include acids such as formic acid and sulfuric acid, and salts such as sodium chloride.

  In the modified natural rubber latex and the modified natural rubber, the graft amount of the polar group-containing monomer is preferably in the range of 0.01 to 5.0% by mass with respect to the rubber component in the natural rubber latex, and 0.01. The range of ˜1.0% by mass is more preferable. When the graft amount of the polar group-containing monomer is less than 0.01% by mass, the low loss and wear resistance of the rubber composition may not be sufficiently improved. Moreover, when the graft amount of the polar group-containing monomer exceeds 5.0% by mass, the physical properties inherent to natural rubber such as viscoelasticity and SS characteristics (stress-strain curve in a tensile tester) are greatly changed. Consequently, the physical properties inherent to natural rubber are impaired, and the processability of the rubber composition may be greatly deteriorated.

  Next, the modified natural rubber was charged in an apparatus to which mechanical shearing force was applied, and mechanical shearing force was applied to generate the polar group-containing monomer in the process of introducing into the natural rubber molecule by graft polymerization. A modified natural rubber having a reduced gel content is obtained. Here, the temperature at the time of applying mechanical shear force (for example, when kneading) using a means for applying mechanical shear force such as plast mill is preferably in the range of 50 to 150 ° C., and the time is 10 to 500 seconds. A range is preferred. When the temperature is less than 50 ° C., the gel content cannot be sufficiently reduced. When the temperature exceeds 150 ° C., the molecular weight is lowered, and the fracture strength, wear resistance, and low loss property are deteriorated. Further, if the time is shorter than 10 seconds, the gel content cannot be sufficiently reduced, and if it exceeds 500 seconds, the molecular weight may be lowered, and the fracture strength, wear resistance and low loss property are deteriorated. There is a concern. A peptizer may be added when applying mechanical shearing force.

  The rubber composition of the present invention is characterized by using the modified natural rubber, and preferably further contains a filler. Here, although the compounding quantity of a filler is not specifically limited, The range of 5-100 mass parts is preferable with respect to 100 mass parts of said modified natural rubber, and the range of 10-70 mass parts is still more preferable. If the blending amount of the filler is less than 5 parts by mass, sufficient reinforcement may not be obtained, and if it exceeds 100 parts by mass, the workability may be deteriorated. Here, as the filler, carbon black and silica are preferable. The carbon black is preferably GPF, FEF, SRF, HAF, ISAF or SAF grade, more preferably HAF, ISAF or SAF grade. On the other hand, as silica, wet silica and dry silica are preferable, and wet silica is more preferable. These reinforcing fillers may be used alone or in a combination of two or more.

  In addition to the above modified natural rubber and filler, the rubber composition of the present invention includes compounding agents commonly used in the rubber industry, such as anti-aging agents, softeners, silane coupling agents, stearic acid, zinc white. Further, a vulcanization accelerator, a vulcanizing agent, and the like can be appropriately selected and blended within a range that does not impair the object of the present invention. As these compounding agents, commercially available products can be suitably used. The rubber composition of the present invention can be produced by blending various modified additives appropriately selected as necessary with the modified natural rubber, kneading, heating, extruding and the like.

  The tire of the present invention is characterized by using the rubber composition, and the rubber composition is preferably used for a tread. A tire using the rubber composition as a tread is excellent in fuel efficiency, fracture characteristics, and wear resistance. The tire of the present invention is not particularly limited except that the rubber composition described above is used for any of the tire members, and can be produced according to a conventional method. Moreover, as gas with which this tire is filled, inert gas, such as nitrogen, argon, helium other than normal or the air which adjusted oxygen partial pressure, can be used.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

<Production Example 1>
(Natural rubber latex modification reaction process)
The field latex was centrifuged using a latex separator [manufactured by Saito Centrifugal Industries Co., Ltd.] at a rotational speed of 7500 rpm to obtain a concentrated latex having a dry rubber concentration of 60%. 1000 g of this concentrated latex is put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 10 ml of water and 90 mg of emulsifier [Emulgen 1108, manufactured by Kao Corporation] are added in advance to N, N-diethylaminoethyl methacrylate. What was emulsified in addition to 0 g was added together with 990 ml of water, and these were stirred at room temperature for 30 minutes while purging with nitrogen. Next, 1.2 g of tert-butyl hydroperoxide and 1.2 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C. for 30 minutes to obtain a modified natural rubber latex.

(Coagulation and drying process)
Formic acid was added to the modified natural rubber latex to adjust the pH to 4.7 to coagulate the modified natural rubber latex. The solid material thus obtained was treated with a creper five times, passed through a shredder and crushed, and then dried at 110 ° C. for 210 minutes with a hot air dryer to obtain modified natural rubber A. From the mass of the modified natural rubber A thus obtained, it was confirmed that the conversion rate of N, N-diethylaminoethyl methacrylate added as a monomer was 100%. In addition, the modified natural rubber was extracted with petroleum ether and further extracted with a 2: 1 mixed solvent of acetone and methanol, but when the extract was analyzed, the homopolymer was not detected. It was confirmed that 100% of the added monomer was introduced into the natural rubber molecule.

<Production Examples 2 and 3>
Instead of 3.0 g of N, N-diethylaminoethyl methacrylate, 2.1 g of 2-hydroxyethyl methacrylate was added in Production Example 2, 1.7 g of 4-vinylpyridine was added in Production Example 3, and the others were Production Example 1. In the same manner, modified natural rubbers B and C were obtained. Further, when the modified natural rubbers B and C were analyzed, it was confirmed that 100% of the monomers added together were introduced into the natural rubber molecules.

<Production Examples 4 to 6>
The resulting modified natural rubbers A, B, and C were masticated at 90 ° C. for 90 seconds using a plast mill [manufactured by Toyo Seiki Co., Ltd.] to obtain modified natural rubbers a, b, and c.

<Production Examples 7-9>
The obtained modified natural rubbers A, B, and C were passed through a prebreaker [manufactured by SPHERE] twice to obtain modified natural rubbers d, e, and f.

  The gel content of the modified natural rubber produced as described above is calculated by the following method, and then a rubber composition having the compounding formulation shown in Table 1 is prepared. Mooney viscosity, tensile strength (Tb), tan δ and abrasion resistance were measured and evaluated. The results are shown in Table 2.

(1) Gel content 0.2 g of modified natural rubber sample was added to 50 ml of toluene and allowed to stand for 24 hours. Toluene insolubles are separated under the condition of 1,000 rpm for 90 minutes. Thereafter, the separated gel component is dried and weighed, and the ratio to the total mass of the modified natural rubber used is calculated and displayed as a percentage by mass.

(2) Mooney Viscosity Mooney viscosity [ML _{1 + 4} (130 ° C.)] was measured at 130 ° C. according to JIS K6300-1: 2001. A smaller Mooney viscosity indicates better processability.

(3) Tensile strength The vulcanized rubber obtained by vulcanizing the rubber composition under normal conditions was subjected to a tensile test according to JIS K6251-1993, and the tensile strength (Tb) was measured. It shows that fracture resistance is so favorable that tensile strength is large.

(4) tan δ
Using a viscoelasticity measuring device manufactured by Rheometrics, tan δ was measured at a temperature of 50 ° C., a frequency of 15 Hz and a strain of 5%. It shows that it is excellent in low-loss property, so that tan-delta is small.

(5) Abrasion resistance Using a Lambourn type wear tester, the amount of wear at a slip rate of 60% at room temperature was measured, and for Examples 1-2 and Comparative Example 1 in Table 2, the reciprocal of the amount of wear of Comparative Example 1 , 100 for Examples 3-4 and Comparative Example 2, the reciprocal of the wear amount of Comparative Example 2 is 100, and for Examples 5-6 and Comparative Example 3, the reciprocal of the wear amount of Comparative Example 3 is 100. displayed. The larger the index value, the smaller the wear amount and the better the wear resistance.

* 1 Table 2 shows the types of modified natural rubber used.
* 2 “Nipsil AQ” manufactured by Nippon Silica Kogyo.
* 3 Degussa, “Si69”, bis (3-triethoxysilylpropyl) tetrasulfide.
* 4 N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.
* 5 N, N'-dicyclohexyl-2-benzothiazolylsulfenamide.
* 6 Diphenylguanidine.
* 7 Dibenzothiazyl disulfide.
* 8 N-t-butyl-2-benzothiazolylsulfenamide.

  From the comparison between the examples in Table 2 and the comparative examples, by using a modified natural rubber having a low gel content obtained by applying a mechanical shearing force by a plastmill or a prebreaker, the processability and fracture of the rubber composition are used. It can be seen that the wear resistance can be greatly improved while maintaining the characteristics and low loss.

Claims (6)

By adding a polar group-containing monomer to natural rubber latex, grafting the polar group-containing monomer to natural rubber molecules in natural rubber latex, further solidifying and drying, and then applying mechanical shearing force Obtained ,
The means for applying the mechanical shear force is at least one of a closed twin-screw kneader, a dry prebreaker, and a twin-screw extruder.
The polar group of the polar group-containing monomer is amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, It is at least one selected from the group consisting of oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group. modified natural rubber.   The modified natural rubber according to claim 1, wherein the graft amount of the polar group-containing monomer is 0.01 to 5.0 mass% with respect to the rubber component of the natural rubber latex. A polar group-containing monomer is added to natural rubber latex, the polar group-containing monomer is graft-polymerized to natural rubber molecules in the natural rubber latex, further solidified and dried, and then subjected to mechanical shearing force .
The means for applying the mechanical shear force is at least one of a closed twin-screw kneader, a dry prebreaker, and a twin-screw extruder.
The polar group of the polar group-containing monomer is amino group, imino group, nitrile group, ammonium group, imide group, amide group, hydrazo group, azo group, diazo group, hydroxyl group, carboxyl group, carbonyl group, epoxy group, It is at least one selected from the group consisting of oxycarbonyl group, sulfide group, disulfide group, sulfonyl group, sulfinyl group, thiocarbonyl group, nitrogen-containing heterocyclic group, oxygen-containing heterocyclic group and alkoxysilyl group. A method for producing modified natural rubber. Rubber composition characterized by using the modified natural rubber according to claim 1 or 2. A tire using the rubber composition according to claim 4 for any tire member. The tire according to claim 5 , wherein the tire member is a tread.