TW201235392A - Resin-coated silica, rubber composition and tire - Google Patents

Abstract

The present invention relates to a resin-coated silica in which a silica, having a specific surface area calculated by evaluating absorption of nitrogen via BET method of 50 to 300 m<SP>2</SP>/g, is sequentially coated by a first coating material and a second coating material, wherein the first coating material includes a phenolic component, and second coating material includes at least one selected from (A) novolac-type phenolic resin and curing agent or (B) resol-type phenolic resin. According to the present invention, it is possible to produce a resin-coated silica having an excellent mixing efficiency with rubber and a beneficial effect of increasing the hardness, a rubber composition having both an effect of improvement of fuel efficiency of automobile due to lowering of rolling resistance of tire and an effect of stabile control, and a tire.

Description

201235392 VI. Description of the invention: [Minghujinshushushu] FIELD OF THE INVENTION The present invention relates to a resin-coated cerium oxide, a rubber composition containing the resin-coated cerium oxide, and a _1&amp; Don't mention the tires of the rubber composition. The present application claims priority based on Japanese Patent Application No. 2010-268709, filed on Jan. 1, 2010, the content of which is hereby incorporated by reference. H Front chair; 3 Background of the Invention In recent years, international interest in the global environment has increased, and from the viewpoint of reducing carbon dioxide emissions, the demand for low fuel consumption of automobiles has gradually increased. The rotational resistance of the tire tread has a large impact on the improvement of the fuel consumption rate of the automobile. Therefore, in order to simultaneously satisfy the environmental and safety, it is necessary to improve the fuel consumption rate of the automobile and the driving stability by reducing the rotational resistance of the tire tread portion. In order to impart abrasion resistance and resilience, a rubbery product in which rubber black is blended is used in the tire tread portion. In this regard, the use of oxide fossils instead of carbon black in riding, in addition to imparting wear resistance and reinforcement, can also improve the fuel consumption rate of automobiles by reducing the rotational resistance of the tires.

In the case of the 妓彳 氧 之 ' 橡胶 橡胶 橡胶 Q Q Q Q Q Q Q Q Q 2012 Q Q 2012 2012 2012 2012 2012 Q 2012 2012 Q 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Q 2012 Q 2012 2012 2012 Q Q Q Q In rubber, it is easy to aggregate and has poor dispersibility. As a result, it is difficult to mix the aerobic particles with the rubber. Also, (4) (4) The effect of imparting hardness to the tire. In order to improve the dispersibility of the cerium oxide particles in the rubber, a method of surface treatment using (4) coupling/oxygen cutting using a cerium-containing sulfide structure has been disclosed (see Patent Document 1). Further, there is disclosed a rubber composition (refer to Patent Document 2) which uses oxygen (4) coated with resin and oxidized resin as a necessary component, and a phenol resin which is a catalyst for phenols and aldehydes. It is obtained by carrying out a reaction in the presence of it. PRIOR ART DOCUMENTS Non-Patent Document Non-Patent Document 1: Polymer Materials. Technical Overview, page 723, (2) Cerium Oxide Enhancement Technology Patent Document Patent Document 1: Japanese Patent Laid-Open Publication No. 08-333481 Patent Document 2: Japanese Patent Laid-Open SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION However, the methods described in Patent Documents 1 and 2 have poor dispersibility of cerium oxide particles in rubber and also have a car by reducing the rotational resistance of the tire. Fuel consumption ♦ improvement and driving * stability is not. Further, oxidation 201235392 The kneading property of Shi Xi and rubber cannot be said to be sufficient and the effect of imparting hardness to the tire is insufficient. The present invention has been made in the above-mentioned circumstances, and an object of the present invention is to provide a "rubber which has excellent effect in imparting hardness to a rubber and which is coated with a resin oxidized hair" and which has a car by reducing the rotational resistance of the tire. A rubber shaft and a tire having improved fuel consumption rate and driving stability. Means for solving the problem In order to solve the above problems, the present invention adopts the following configuration. That is, the resin-coated oxygen (four) of the present invention will be borrowed. An oxide 11 having a specific surface area of 5 G to m 2 /g is adsorbed by the first coating material and the second covering material, and the first "covered material contains a Lai" And the second covering material comprises at least one of (4) a secret varnish type trans fat and a hardener, and (b) a lion (four) trans fat. In the resin-coated oxidized stone of the present invention, it is preferred that the first coating material contains a curing agent. Further, in the resin-coated oxidized stone of the present invention, it is preferable that the first covering material contains a decane coupling agent. Further, the rubber composition of the present invention is characterized by comprising the resin-coated cerium oxide and rubber of the present invention. Further, the tire of the present invention is characterized in that the rubber composition of the present invention described above is used in a tire tread portion. Advantageous Effects of Invention According to the present invention, it is possible to provide a oxidized stone of a financial resin which is excellent in kneading property with rubber and which is excellent in hardness effect by 201235392. Mine: The present invention can provide a rubber composition and a tire which can reduce the rotation of the tire, the fuel of the vehicle, and the improvement of the steering rate and the stability of the driving. [Embodiment 3] The embodiment for carrying out the invention &lt; resin-coated cerium oxide&gt; The resin-coated oxidized stone of the present month is a nitrogen adsorption specific surface area measured by the BET method of 5 G to m2/ The oxygen cut of g is sequentially covered by the first covering material and the second covering material. (Yttrium Oxide) The oxidized oxide used in the resin-coated oxidized oxide of the present invention may be wet oxidized # or dry oxidized therein, and the reinforcing effect is relatively high, and wet yttrium oxide is preferred. . In the present publication, "the gas adsorption specific surface area measured by the BET method" means that the surface of the powder particles is adsorbed with nitrogen gas, and the pressure and the amount of adsorption from the time are measured by the single molecule adsorption method. The specific surface area obtained by the amount. The nitrogen adsorption specific surface area measured by the BET method is preferably 5 〇 to 3 〇〇 mV _ 〜 23, preferably 115 to 2 lW/g. When the specific surface area of the nitrogen oxide adsorption surface is less than or equal to the lower limit value, the reinforcing effect on the rubber is excellent. On the other hand, when the upper limit is less than or equal to the above, the oxides in the rubber are excellent in dispersion. 201235392 The cerium oxide system may be used singly or in combination of two or more. (First Covering Material) The first covering material contains a class. In the present invention, the term "phenol" means an aromatic mercapto compound obtained by substituting a hydroxyl group for a hydrogen atom of an aromatic hydrocarbon ring. Examples of the phenols include phenol, resorcin, indole, dinonylphenol, propylbenzene, butylbenzene, octylbenzene, propylbenzene, phenylbenzene, and bromophenol. , bisphenol A, bisphenol F, cardanol, such as cashew nuts shell oil, gallic acid, butyl scent and paint. Among them, it is easy to coat cerium oxide due to liquid form and is economically advantageous, and cresol, allyl phenol, cardanol and, for example, nut shell oil are preferred, and cresol and cardanol are more preferred. Among the cresols, ortho-cresol is preferred. Among the allyl phenols, o-allyl benzene is preferred. The phenol type may be used alone or in combination of two or more. The content of the phenol in the first coating material (the solvent and the dispersion medium) is preferably 40% by mass or more and less than 100% by mass based on 100% by mass of the first coating material (solvent and dispersion medium). It is more preferably 60% by mass or more and less than 100% by mass, and may be 100% by mass. When the content of the phenol is more than the lower limit, the polarity of the surface of the cerium oxide can be easily reduced. Further, the second coating material can be easily used to coat the cerium oxide which has been coated with the first covering material. The first covering material may contain components other than phenols. In the resin-coated cerium oxide of the present invention, the first covering material 201235392 preferably contains hard _. By using hard (four) in combination, the rubber-containing alloy sulfur (4) containing the resin-covered oxygen is cut, and the first (four) material system and the first coating material simultaneously undergo a hardening reaction, and the first covering material and the second covering material are integrated. The effect is further improved. In the present invention, the term "hardener" means a compound which is crosslinked by a hydrogen atom or a phenolic hydroxyl group of an aromatic aromatic ring. Examples of the curing agent include hexamethylene hexamethoxyf-based trimeric amine, formic acid, formic acid, ethylene bis, tris, 4,4,-diaminodiphenylcarbamate, acetaldehyde ammonia, Resole type phenol resin, urethane resin, epoxy resin, and the like. Among them, hexamethyleneamine, hexamethoxymethylmelamine, and 4,4,-diaminodiphenylmethane are preferred because of the ease of the hardening reaction, and hexamethyleneamine is particularly preferred. The hardeners may be used alone or in combination of two or more. The content of the curing agent in the first covering material (removal solvent and dispersion medium) is preferably 5 parts by mass to 5 parts by mass based on 100% by mass of the phenol, more preferably 5 to 20 parts by mass. When the content of the curing agent is at least the lower limit value, the effect of integrating the first covering material and the second covering material is improved, and when the obtained rubber composition is made into a tire, good hardness can be easily obtained and driving stability can be achieved. Sex also improved. On the other hand, when it is larger than the upper limit of the preferable value, the effect of imparting hardness according to the increased component and improvement in driving stability cannot be observed. When the upper limit is preferred, the cost can be reduced. Further, in the resin-coated cerium oxide of the present invention, the first coating material preferably contains a decane coupling agent. By using a decane coupling agent in combination, the affinity between cerium oxide and phenol is improved, and the enthalpy of cerium lanthanum and the first covering material are improved. #As the Shi Xi siu coupling agent, an amine group such as 3 amine propyl triethoxy zeshi, N_ phenyl 3 propyl propyl di oxime oxime, etc.; Dimethicone, and 2,(3,4-epoxycyclohexyl)ethyltrimethoxy oxasulfuric acid, etc.; vinyl trimethoxy Wei and "ethylene triethoxylate" Base crucible; 3 - methacryloxypropyl methyl dimethoxy decane and 3-methyl propylene oxypropyl triethoxy decane, etc. a styryl decane, such as a styryl trioxane, or a hydrothiodecane such as 3-hydrothiopropylmethyldimethoxydecane or 3-hydrothiopropyltrimethoxydecane; a thioether oxime such as (triethoxydecyl propyl) tetrasulfide, etc., wherein the adhesion of cerium oxide to the first coating material is further improved, and 3-aminopropyltriethoxy zexi The decane coupling agent may be used alone or in combination of two or more. The oxime coupling agent containing a polysulfide structure (sulfur atom) described in Patent Document 1 is expensive. Moreover, there is a problem of high cost in order to obtain a tire. However, in the resin-coated oxidized granule of the present invention, it is not necessary to use a sulphur coupling agent. Even when the Shi Xixuan• coupling agent is used, the above-mentioned usual The decane coupling agent can also obtain the effect of improving the adhesion between cerium oxide and the first coating material instead of using the sulfonium coupling agent containing a sulfur atom, and can reduce the cost. The first coating material (solvent, dispersion medium) The content of the scorpion coupling agent in the medium is preferably from 5 to 700 parts by mass, more preferably from 30 to 350 parts by mass, per 100 parts by mass of the phenol. The content of the shi xia xiao coupling agent is preferably a lower limit. When the value is more than or equal, the affinity between the oxidized stone and the hop 9 201235392 is improved, and the adhesion between the oxidized oxidized stone and the first coating material is improved. When the content of the decane coupling agent is preferably less than or equal to the upper limit, the rupture is not caused. The strength of the rubber product such as strength is lowered. (Second coating material) The second coating material contains at least one of (A) a novolac type phenol resin and a curing agent, and (B) a novolac type phenol resin. The second covering material contains (A) a novolac type phenol resin and a hardener, and (B) a novolak type phenol resin; or (A) a novolac type phenol resin, and a hardener and B) Any one of the resol type phenol resins. (A) Novolac type phenol resin and curing agent As a novolac type phenol resin, it is possible to react a phenol with an aldehyde in the presence of an acid catalyst. Further, it is also possible to use a novolac type phenol resin obtained by modifying a reactant of a phenol and an aldehyde, such as nut shell oil, tung oil, and rosin, in the presence of an acid catalyst. The term "aldehyde" means a compound having at least one hydrogen atom in the carbonyl group, that is, a compound having a methyl group-CHO. Phenols can use stupid phenol, resorcinol, indophenol, diphenyl benzene, propyl phenol, butyl phenol, octyl phenol, phenyl phenol, bromophenol, bisphenol A, bisphenol F, cashew nuts Phenol, such as nut shell oil, gallic acid, eugenol and urushiol. The phenols may be used alone or in combination of two or more. The aldehydes can be used in the form of formaldehyde, p-quinone, trioxane, glyoxal, styrene, and lysine. The above-mentioned brewing type may be used alone or in combination of two or more. 10 201235392 /, because it is easier to reduce the rotational resistance of the tire and the U consumption rate of the steam A/.... when it is made into a tire, as a phenol, it is a phenol, a formazan, a cardanol. , butyl floc ^ ^ phenol, octyl phenol, and bisphenol hydrazine is preferred, with phenol, and cardanol is preferred. &amp; β , as the aldehyde ' is preferably formaldehyde, and is preferably formaldehyde, and more preferably formaldehyde. ★Western catalysts can be exemplified by hydrochloric acid, sulfuric acid, acid, formic acid, acetic acid, grass, butyl, lactic acid, benzenesulfonic acid, p-toluenesulfonic acid, boric acid, or zinc chloride or ethyl zinc. Salt and so on. The acid catalysts may be used singly or in combination of two or more. The varnish-type resin may be used alone or in combination of more than one. The octa-coated material contains a smear-type resin and a hardener, and the varnish-type lyophilized material in the second coating material (solvent removal medium) is used when there is no (B) soluble acid-type resin. The content of the second coating material (removal solvent, dispersion medium) relative to yttrium (9)% by mass is preferably 30 to 99% by mass, preferably 60 to 98% by mass, and more preferably 7 to 95% by mass. good. When the content of the phenolic acid varnish type-age resin is more than the lower limit value, the kneading ability of the oxidized stone enamel to the rubber is increased by 4, and when the tire is formed, it is easy to reduce the driving property of the tire. When the content of the varnish-type resin is preferably at most the upper limit, the breaking strength, the hardness, and the like are not lowered as the physical properties of the rubber product. The hardening agent of the component (A) may be the same as the hard (four) of the above-mentioned first covering material. Its towel, because the hardening reaction is easy to carry out well, it is better to use hexamethylenetetramine, hexamethoxymethylmelamine, 11 201235392 and 4·4'-diaminodiphenylcarbendrie, and it is particularly preferable to hexamethylenetetramine. . The hardeners may be used alone or in combination of two or more. The content of the hardener in the second covering material is preferably 4 parts by mass, more preferably 1 part by mass, more preferably 5 parts by mass to 2 parts by mass, based on 1 part by mass of the enzyme acid varnish type resin. When the content of the curing agent is at least the lower limit value, the effect of imparting hardness to the rubber and the finished product after vulcanization is enhanced. Further, when the tire is made, it is easy to reduce the rotational resistance of the tire and the driving stability of the automobile. On the other hand, even if it is larger than the preferred upper limit value, the hardness effect imparted to the tire according to the increased component and the improvement in driving stability cannot be observed. When the upper limit is less than the upper limit, it is possible to reduce the cost. (Β) Novolac type phenol resin As the novolak type phenol resin, a phenol and an aldehyde can be reacted in the presence of a base catalyst. Further, a resol type phenol resin obtained by modifying a reactant of a phenol and an aldehyde, such as nut shell oil, tung oil, and rosin, in the presence of a catalyst may be used. These resol type phenolic resin resins are self-hardening. Examples of the phenols and aldehydes in the description of the novolac type phenol resin are the same as the aldehydes and the aldehydes. "When it is made into a tire, it is easier to reduce the rotational resistance of the tire and the driving stability of the car. As the phenol, phenol, indophenol, cardanol, butylphenol and octylphenol are preferred. Phenol and cardanol are more preferred. As the aldehyde, formaldehyde and formaldehyde are preferred, and formaldehyde is more preferred. 12 201235392 The catalysts include hydroxides of alkali metals such as sodium hydroxide and lithium hydroxide, hydroxides of alkaline earth metals such as hydroxide and barium hydroxide; ammonium hydroxide; diethylamine and An amine such as ethylamine, triethanolamine, ethylenediamine or hexamethyleneamine. These alkali catalysts may be used alone or in combination of two or more. The resol type phenol resin may be used singly or in combination of two or more. When the second covering material contains (B) a novolac type phenol resin and does not contain (A) a varnish-type varnish resin and a hardener, the second covering material (solvent-removing solvent, in the form of a smear) The content of the bismuth resin is preferably from 30 to 100% by mass based on 1% by mass of the first coating material (removal solvent or dispersion medium), and is 70 to 1 Torr. /. Preferably, it is more preferably 1% by mass. When the content of the novolak-type phenol resin is at least the lower limit value, the kneading ability of the oxidized stone to the rubber is improved. Moreover, when the tire is made, it is easy to reduce the rotational resistance of the tire and the driving stability of the automobile. The first covering material may be a phenolic phenol resin and a hardener, (B) a melamine resin, a gland tree Ja, an oxygen stalk grease, a urethane resin, or a yeast resin. , unsaturated poly S 曰 resin 'polyethylene, poly bis, polyethylene, polystyrene, polyethylene vinegar, ABS resin (acrylonitrile butadiene styrene copolymer), AS resin (C Dilute nitrile styrene copolymer), acrylic resin, polyamide resin, poly(anthraquinone resin), poly-p-(tetra)ethylenedi(tetra) sulphate, poly(p-butylene) vinegar, polyphenylene sulfide resin, polyester and fine fat (C) resin. In order to promote the curing reaction of the novolac type phenol resin and the curing agent, a curing catalyst such as calcium hydroxide may be used as the second coating material. When the resin (c) is used in combination, the total content of the second coating material (solvent and dispersion medium) (the total content of the novolac type phenol resin and the novolak type phenol resin) / (total resin content) is determined by the mass ratio. When the mass ratio is more than the lower limit value, the breaking strength, the hardness, and the like are not lowered as the physical properties of the rubber product, and the kneading performance of the cerium oxide to the rubber is improved. When the tire is formed, it is easy to reduce the rotational resistance of the tire and the driving stability of the automobile. (Production of resin coated oxidized oxide enamel) The resin-coated cerium oxide coated according to the present invention can be used by using the first covering material. The second coating material is produced by sequentially coating the above-mentioned oxidation 7. Specifically, a method of mixing the oxygen-cutting material and the first coating material and then adding the first coating material may be mentioned. The amount of the antimony contained in the oxidized slightly coated coating material is preferably 0.5 to 50 parts by mass, and more preferably (4) parts by mass, based on 1 part by mass of the oxidized oxide. Oxygen The larger the specific surface area of Shixi, the more the coating amount of the first coating material is. The lanthanum contained in the ruthenium coating material is preferably a lower limit value or more, and the polarity of the surface of the oxidized surface is easily reduced. By using the second coating material to coat the second coating material, the oxygen cut m which is covered by the first covering material is preferably below the upper limit of the preferred value, 14 201235392 p and the driving force of the car When the tire is made, it is easy to reduce the stability of the rotation of the tire. When the first covering material contains a broken coupling agent, the smear-coated material

The amount of coating is based on 100 parts by mass of cerium oxide, and the decane coupling agent contained in the coating material coated by the gas emulsification is preferably 〇. 3 ~ 2 Q temporarily I, negative aliquot is preferably 1 ~10 parts by mass is better. When the ceramsite coupling agent contained in the coating material is preferably a lower limit or more, the adhesion between the cerium oxide and the first coating material is easily described. On the other hand, even if it is larger than the preferred upper limit, the adhesion of the cerium oxide to the first covering material in accordance with the increased amount thereof cannot be observed. When the upper limit is preferred, the cost can be reduced. The first covering material contains (A) acid varnish type resin and does not contain (B) soluble and removable resin. The coating amount of the first covering material is oxidized with respect to 100 parts by mass of cerium oxide. The novolac type phenol resin contained in the coating material to be applied is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass. When the novolak-type phenol resin contained in the coating material is preferably at least the lower limit value, the kneading property of the cerium oxide to the rubber is improved. When the novolak-type phenol resin contained in the coating material is preferably at most the upper limit value, the breaking strength, the hardness, and the like are not lowered as the physical properties of the rubber product. When the novolac type phenol resin is in the above preferred range, it is easy to reduce the rotational resistance of the tire and the driving stability of the automobile when the tire is formed. When the second covering material contains (B) a resol type phenol resin and does not contain (A) a novolac type phenol resin and a curing agent, the coating amount of the second covering material is 15 201235392 based on 100 parts by mass of the oxygen emulsified enamel. It is preferable that the soluble riding weight of the above-mentioned coated material coated in the rolled mash is preferably 5 parts by mass to 5 parts by mass, and more preferably 1 part by mass to 3 parts by mass. When the soluble _ type _ fat contained in the coating material is more preferably equal to or less than the lower limit value, the kneading property of the oxygen dicing is improved. When the soluble lysate contained in the coating material is at most preferably the upper limit or less, the breaking strength, the hardness, and the like are not lowered as the physical properties of the rubber product. When the resol type phenol resin resin is in the above preferred range, it is easy to reduce the rotational resistance and the driving stability when the tire is formed. When the second covering material contains both (A) a novolac type phenol resin and a curing agent, and (B) a novolak type phenol resin, the coating amount of the second covering material is 100 parts by mass of cerium oxide. The total of the novolak-type phenol resin and the soluble age-type resin contained in the coating material coated with cerium oxide is preferably 0.5 to 50 parts by mass, more preferably 1 to 30 parts by mass. When the total of the novolac type phenol resin and the novolac type phenol resin contained in the coating material is preferably at least the lower limit value, the kneading ability of the oxide to the rubber is improved. When the total amount of the varnish-type oxime resin and the resol-type phenol resin contained in the coating material is preferably at most the upper limit value, the breaking strength, the hardness, and the like are not lowered as the physical properties of the rubber product. The total amount of the phenolic varnish test resin and the soluble brewing type resin is in the above-described preferred range. When the tire is formed, the valley has both reduced the rotational resistance of the tire and the driving stability of the automobile. The first covering material and the second covering material may be each diluted or dispersed using a suitable solvent or dispersion medium as necessary. 16 201235392 For solvent or dispersion medium, water, sterol, propyl ketone, and ethyl ketone can be used. When the first coating material contains a decane coupling agent, the decane coupling agent may be preliminarily mixed with other components contained in the first coating material to be mixed with cerium oxide, and the decane coupling may be used. After the mixture is separately mixed with cerium oxide, it is mixed with other components contained in the first covering material. A mixture of cerium oxide and each coating material can be a device such as a batch mixer or a continuous mixer. These devices may be used at room temperature or if necessary, for heating. In particular, in the case of a solid material for each covering material, it is preferable to use a heating operation because the mixing operation can be easily performed. The oxidized rock obtained by adding the second covering material and mixing may be dried as necessary using a well-known dryer or the like. The drying temperature and drying time at this time may be appropriately determined depending on the solvent or dispersion medium, the amount of dilution of the material, and the like. Preferably, the phenolic material in the first covering material is selected from the group consisting of phenol, resorcinol, deuterium, dinonylphenol, propylphenol, butylphenol, octylphenol, allylphenol, phenylphenol, (A) Novolac in the second covering material, at least one of a group consisting of bromophenol, bisphenol A, bisphenol F, cardanol, nut shell oil, gallic acid, butyl scent, and lacquer Among the phenolic resins and hardeners, the varnish type #resin will be selected from the group consisting of benzene, dioxin, meth, xylene, propyl, butyl benzene, octyl benzene, phenyl. Benzene, Aussie, Double A, Double 酴F, cashew nuts, such as nutshell oil, 17 201235392 Gallic acid, τ 酴 酴 and lacquer _ at least _ of the group _ and selected from m And at least one of a group consisting of tris, b, benzoic acid, and lysine, reacted in the presence of an acid catalyst, and the hardener is selected from the group consisting of hexamethylenetetraamine, hexamethoxymethylmelamine, For formaldehyde, formaldehyde, glyoxal, tri-π-alkane, 4,4,-diaminodiphenylcarbamate, B (tetra), soluble secret lysine, urethane tree At least one of the group consisting of an epoxy resin and a ^. In the first covering material as a hardening agent, the reinforcing force σ may be selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, p-formaldehyde, formaldehyde, glyoxal, tri-n-alkane, 4,4,-diaminodiphenyl At least one selected from the group consisting of methane, acetaldehyde ammonia, resol type phenol resin, urethane resin and epoxy resin, as a decane coupling agent, may be selected from 3-aminopropyltriethoxydecane , an amino decane such as fluorenyl-phenyl-3-aminopropyltrimethoxy decane; hydrazine propylene oxide propyl trimethoxy decane; and 2-(3,4-epoxycyclohexyl)ethyltrimethoxy Ethylene decane such as decane or the like; vinyl decane such as vinyl trimethoxy decane and vinyl triethoxy decane; 3-methacryloxypropylmethyl decyloxy decane and 3-methyl Methyl propylene oxime oxime, such as acryloxypropyl triethoxy decane; stupid benzyl decane, etc.; styrene-based trimethoxy oxycarbazide; 3-hydrothiopropylmethyl a hydrothiodecane such as dimethoxydecane or 3-hydrothiopropyltrimethoxydecane; bis(triethoxydecylpropyl)tetralin or the like At least one of the group consisting of silane-ether. Preferably, the phenolic material in the first covering material is selected from the group consisting of phenol, stupid, methyl, xylene, propyl benzene, butyl benzene, octyl benzene, allyl phenol, benzene At least one of a group consisting of phenol, bromophenol, bisphenol A, bisphenol F, cardanol, 201235392 such as nut shell oil, gallic acid, eugenol and urushiol, and as a second covering material (B) Soluble-looking resin, selected from the group consisting of phenol, resorcinol, indophenol, dimethylphenol, propylphenol, butylphenol, octylphenol, phenylphenol, bromophenol, bisphenol A, bisphenol F, cashew nut, such as nut shell oil, gallic acid, butyl fragrant and lacquer, at least one of the phenols selected from the group consisting of formaldehyde, paraformaldehyde, trioxane, and ethyl A mixture of at least one of the group consisting of scorpion acid and succulent is reacted in the presence of a base catalyst. As the hardener of the first covering material, it may be selected from the group consisting of hexamethylenetetramine, hexamethoxyguanidino melamine, p-nonaldehyde, formaldehyde, glyoxal, triterpenoid, 4,4'-diaminodiphenyl At least one selected from the group consisting of methane, acetaldehyde ammonia, a resol type phenol resin, an amine phthalate resin, and an epoxy resin, and as a decane coupling agent, may be selected from the group consisting of 3-aminopropyltriethoxydecane, Amino decane such as N_phenyl_3_aminopropyl decyloxydecane; 3-glycidoxypropyltrimethoxydecane, and 2-(3,4·epoxycyclohexyl)ethyl a cyclodecyl stone such as a decyloxydecane; a vinyltrimethoxy group; a vinyl decane such as triethyl ethoxy sulfonate; and a 3-methyl propylene methoxy propyl methyl dimethyl hydride; Oxygen oxime and 3-methyl propylene oxypropyl triethoxy wei, etc., methyl styrene oxide; styrene-based trimethoxy (tetra), etc. Sulfur such as hydrogenthiopropyl propyl dimethoxy (tetra) and 3-hydrothiopropyl propyl sulfoxide; sulphur such as bis(triethoxy propyl) tetrasulfide Mystery At least one of the group consisting of. Preferably, the phenolic material in the first covering material is selected from the group consisting of phenol, isophthalene, acenaphthene, dimethyl acetonate, propyl benzene H, octyl benzene, 19 201235392 allyl phenol, phenyl At least one of a group consisting of phenol, bromophenol, bisphenol A, bisphenol F, cardanol, nut shell oil, gallic acid, eugenol, and urushiol, and (A) phenolic resin of the second covering material Among the varnish type phenol resin and hardener, the novolak type phenol resin will be selected from the group consisting of phenol, resorcinol, indophenol, dinonylphenol, propylphenol, butylphenol, octylphenol, phenylphenol, and bromine. a phenol selected from the group consisting of phenol, bisphenol A, bisphenol F, cardanol, nut shell oil, gallic acid, eugenol and urushiol, and is selected from the group consisting of formaldehyde, paraformaldehyde, and triterpenoids. An aldehyde which is at least one of a group consisting of alkane, glyoxal, benzaldehyde, and salicylaldehyde is reacted in the presence of an acid catalyst, and the hardener is selected from the group consisting of hexamethylenetetramine and hexamethoxyfluorene. Melamine, paraformaldehyde, formaldehyde, glyoxal, trioxane, 4,4,-diaminodiphenylmethane At least one of the group consisting of acetaldehyde ammonia, a resol type phenol resin, a urethane resin, and an epoxy resin, and the (B) resol type phenol resin of the second covering material is selected from the group consisting of phenol and Hydroquinone, indophenol, xylenol, propylphenol, butylphenol, octylphenol, phenylphenol, bromophenol, bisphenol A 'bisphenol F, cardanol, such as nut shell oil, gallnut An aldehyde having at least one selected from the group consisting of acid, eugenol, and urushiol, and an aldehyde selected from the group consisting of formic acid, terpene, secondary, ethylene, benzophenone, and arsenic It is obtained by reacting it in the presence of a base catalyst. In the first covering material as a hardening agent, it may be selected from the group consisting of hexamethylenetetramine, hexamethoxyguanidino melamine, p-Alpha, methicone, oxalic acid, tri-sodium bromide, 4,4-aminodiphenyl ketone. At least one kind of group consisting of ammonia acetate, soluble secret age resin, urethane formic acid, resin and epoxy resin, 20 201235392 is a decane coupling agent, which may be selected from 3-aminopropyltriethoxy group Amine, N-phenyl-3.aminopropyltrimethoxy(tetra), etc.; amine-based; 3-glycidoxypropyltrimethoxy sylvestre; and 2_(3,4-epoxycyclohexyl) Ethylene decane such as trimethoxy decane; vinyl decane such as vinyl trimethoxy decane or vinyl triethoxy decane; 3-methyl propylene methoxy propyl methyl dimethoxy decane and Methyl propylene decyl oxane such as 3-methyl propylene methoxy propyl triethoxy decane; styryl decane such as p-styryl trimethoxy decane; 3-hydrothiopropyl methyl dimethyl a thioxanthene such as decyloxydecane or 3-hydrothiopropyltrimethoxy oxalate; or a bis(triethoxydecylpropyl)tetrasulfide At least one of the group consisting of thioethers. Preferably, the g classification of the first covering material is at least one selected from the group consisting of cresol, allyl phenol, cardanol and, for example, nut shell oil, and (A) novolac type of the second covering material. Among the phenol resin and the hardener, the varnish type varnish type resin varnish type age resin is selected from the group consisting of benzene, cresol, cardanol, butyl phenol, octyl phenol and bisphenol A. At least one phenol is reacted with an aldehyde selected from the group consisting of formaldehyde and/or formaldehyde, in the presence of an acid catalyst, and the hardener is selected from the group consisting of hexamethylenetetramine, hexamethyleneoxymethylmelamine, and 4 At least one of the group consisting of 4'-diaminodiphenylnonane. In the first covering material as a hardening agent, it may be selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, p-formic acid, brewing, oxalic acid, tris-sigma, 4,4'-diaminodiphenyl At least one selected from the group consisting of acetaldehyde ammonia, a resol type phenol resin, a urethane resin, and an epoxy resin, and as a decane coupling agent, may be selected from 3-aminopropyltriethoxy group. Hydrane, 21 201235392 Amino decane such as N-phenyl-3-aminopropyltrimethoxydecane; 3 glycidoxypropyltrimethoxy sinter, and 2_(3,4·epoxycyclohexyl) a vinyl oxane such as an epoxy group such as ethyltrimethoxy oxalate or a vinyl sulfonate such as a (10)-based trimethoxy-propane or a vinyltriethoxy decane; and a 3-methacryloxypropyl fluorenyl dimethyloxy group; Methyl propylene decyl oxane such as decane and 3-methyl propylene methoxy propyl triethoxy decane; styrene based styrene based on styryl trimethoxy decane; thiopropyl propyl group Dimethyl oxyzolone and thioethers such as 3-hydrothiopropyltrimethoxywei (10) thiocarbazone: bis(triethoxyweiylpropyl)tetrasulfide At least one of the group consisting of. Preferably, the phenol in the first covering material is at least one selected from the group consisting of cresol, allyl age and cashew nut oil, and (B) soluble as the second covering material. The secret gamma resin is selected from the group consisting of benzodiazepine, acetaminophen, lumbar filament, T-base secret and octise ride. The _贞 is selected from the group consisting of f and/or 曱__, in the catalyst test. In the presence of it to make it react. In the first covering material as a hardening agent, it may be selected from the group consisting of hexamethylenetetramine, hexamethyleneoxymethylmelamine, palladium disk, decanoic acid, ethylene bismuth, and tris-5, 4,4'-aminodiphenyl. At least one of the group consisting of methyl ketone, ethyl sulphate, soluble age-type saplings, urethane resin and epoxy resin, as a Shi Xi siu coupling agent, may be selected from the group consisting of 3 - amine C Amino decane such as triethoxy wei, N-phenyl-3-aminopropyl trimethoxy decane; hong tong propyloxypropyl tri methoxy wei, and 2 (3, 4 · Epoxycyclohexyl)ethyltrimethoxysulfene, etc., such as vinyl decane, such as ethylene, trimethoxy, and ethylenetrimethoxydecane; 3-mercaptopropoxypropylpropyl基二22 201235392 methoxy oxime and 3-mercaptopropene oxypropyl triethoxy oxysulphate, such as methacrylic yoghurt kiln kiln, p-styryl trioxane, etc. Benzethyl decane; 3-hydrothiopropyl decyl dimethoxy decane and 3-thiol propyl trimethoxy oxysulfanyl thioxanthene; bis(triethoxy decyl propyl propyl) Base) four Xi sulfide stone burned ether group composed of at least one. Preferably, the phenol in the first covering material is at least one selected from the group consisting of indophenol, allylphenol, cardanol and, for example, nut shell oil, and (A) novolac as the second covering material. Among the phenol resins and hardeners, the varnish-type resin is selected from the group consisting of phenols of at least one group consisting of idyllic, azolla, cashew, butyl phenol, octylphenol, and bisphenol A. And the aldehyde selected from formaldehyde and/or paraformaldehyde is reacted in the presence of an acid catalyst, and the hardener is selected from the group consisting of hexamethylenetetramine, hexamethoxymethyl melamine, 4, 4 At least one of the group consisting of '-diaminodiphenylmethane, and (B) of the second covering material is soluble: the resin is selected from the group consisting of phenol, cresol, cardanol, butyl phenol and a phenol of at least one group consisting of octylphenol and an aldehyde selected from furfural and/or furfural, which are reacted in the presence of a base catalyst &lt;, in the first covering material as a curing agent, may be selected from the group consisting of hexamethylenetetramine, hexamethoxyguanidino melamine, para-formaldehyde, formaldehyde, glyoxal, triterpenoid, 4,4,-diaminodi At least one of a group consisting of phenylmethane, acetaldehyde ammonia, a soluble phenolic phenol resin, a urethane resin, and an epoxy resin, and as a decane coupling agent, may be selected from the group consisting of 3-aminopropyltriethoxy Amino decane, such as decane, N-phenyl-3-aminopropyltrimethoxy decane, etc.; hydroxyglycidylpropyltrimethoxy wei, and 2_(3,4 epoxycyclohexyl) Trimethyloxy 23 201235392 Oxidoxy money of Shi Xizhuo; and (10) base of vinyl trimethoxy Wei and ethylene triethoxy Wei; 3 • methyl propyl oxypropyl methyl dimethyl a methacrylic acid and a methyl methacrylate oxime such as a methacryloxypropyltriethoxy group; a styryl group of a styrene-based trimethoxy wei; and a thiol group; Hydroxythiol of propylmethyldimethoxylyl and 3•hydrothiopropyldimethoxywei; thioether decane such as bis(triethoxycarbonylpropyl)tetrasulfide Into groups of at least one. Preferably, the phenol of the first covering material, cresol or cardanol is among the (A) novolac type phenol resin and the hardener of the first covering material, and the novolak type phenol resin is phenol and/or cardanol. It is formed by reacting formaldehyde with an acid catalyst in the presence of an acid catalyst, and the hardener is hexamethylenetetramine or 4,4,diaminodiphenylmethane. Further, hexamethyleneamine may be added as a hardener to the first covering material, and 3-aminopropyltriethoxysulfuric acid may also be added as a sulphur coupling agent. Alternatively, it is preferably a phenol in the first covering material, which is a nonylphenol or a cardanol, and a (B) resol type phenol resin in the second covering material, which is a phenol and/or a cardanol and a furfural in a base catalyst. The presence of the reaction makes it possible. It is also possible to add hexamethyleneamine as a hardener to the first covering material, and also to add 3-aminopropyltriethoxysulfonium as a oxime coupling agent. Further, it is preferable that the first covering material is a kind of a variety of materials, such as a crepe or a cashew nut, among the (A) novolac type phenol resin and the hardener of the second covering material, the 'novolak type phenol resin is phenol and/or Or the reaction of cardanol and furfural in the presence of an acid catalyst, and the hardener is hexamethylenetetramine or 4,4,diaminodiphenylmethane, and (B) the novolak type phenol resin is phenol. And/or cardanol and formic acid are reacted in the presence of a catalyst. It is also possible to add hexamethylenetetraamine as a hardener in the first quilt 24 201235392, and it is also possible to add 3-aminol triethoxy decane as a decane coupling agent. ~~ &lt;Rubber Composition&gt; The rubber composition of the present invention contains the cerium oxide and rubber coated with the above-described present invention. 9 (Rubber) As the rubber, natural rubber; i-olefin rubber such as stupid ethylene butadiene rubber, polyisoprene rubber, polybutadiene rubber, and ethylene butadiene rubber; ~~ Rubber The content of the ruthenium oxide coated with the resin in the composition is preferably 10 to 200 parts by mass, more preferably 3 to 15 parts by mass, per 100 parts by mass of the rubber. When the content of the resin-coated oxidized oxide is preferably equal to or less than the upper limit, the oxygen (4) coated with the resin and the rubber are easily blended well. When the content of the oxygen (4) coated with the resin is preferably at least the lower limit value, the rotational resistance of the tire can be lowered when the tire is formed. Further, the content of the oxygen (10) coated with the resin is in the above-described preferred range, and the wheel material is more versatile (4), which reduces the rotational resistance of the tire and the driving stability of the automobile. The rubber composition may also contain a component other than the resin-coated oxidized oxide and the rubber. In the rubber composition, in addition to the oxide-coated oxide oxide, a reinforcing material of carbon black, hydrogen peroxide, oxygen, carbonic acid, and a clay = may be used in combination. These reinforcing materials can be surface treated using the well-known Wei coupling yeast even if the surface: the processor'. 25 201235392 In addition, a reinforcing resin such as a phenol resin, a hardener such as hexamethyleneamine or hexamethoxymethylmelamine, or sulfur, and 4,4'-diaminodiphenyl can be used as the rubber composition. A rubber crosslinking agent such as decane; a vulcanization accelerator, an antioxidant, a plasticizer, various oils, waxes, stearic acid, and oxidized words, and the like, which are commonly used in the rubber industry. The rubber composition (unvulcanized rubber composition) in an unvulcanized state can be a device using a Banbury mixer, a roll machine, a kneader or the like by using a resin-coated cerium oxide, a rubber, and other optional components as necessary. Perform kneading to manufacture. Further, by filling the rubber composition in an unvulcanized state in a predetermined mold or the like, it is preferably subjected to heat treatment (vulcanization) at 130 to 180 ° C for 5 to 60 minutes to obtain a rubber composition in a vulcanized state (vulcanized rubber composition). ()). The rubber composition of the present invention can be used for applications such as tires, conveyor belts, rubber crawlers, anti-vibration rubbers, hose mats, and marine fences. Among them, it is preferable to use it as a tire, and it is particularly preferable as a tire tread. &lt;Tire&gt; The tire of the present invention is used in the tire tread portion of the rubber composition of the present invention. Such a tire can be manufactured by a usual method. Specifically, it is possible to use the rubber composition of the present invention in an unvulcanized state and to process it into a predetermined shape of the tire tread portion, and to use a rubber composition which has been prepared into a suitable tire for the tire in an unvulcanized state and has been processed. Those who have their respective predetermined shapes are formed by laminating a tire molding machine to form a green tire (unvulcanized 26 201235392 state) and heating it in a vulcanizer to add dust. In the manufacture of an unvulcanized rubber composition, the oxygenation of the invention is compared to the use of a decane coupling agent having a polysulfide structure of the first ten people or an oxygen cut after the surface treatment of the phenol resin. Oxygen = good adhesion to rubber at night. X, compared with the vulcanized rubber composition using cerium oxide previously subjected to the surface treatment, using the resin-coated oxidized rubber sulphide of the present invention, the fuel consumption rate of the automobile is reduced by reducing the rotational resistance of the tire The improvement and driving stability are both excellent and the hardness is excellent. The reasons for these are as follows. In the resin-coated cerium oxide of the present invention, the cerium oxide is directly coated with the phenol-containing first covering material. The phenol type has a hydrophilic phenolic hydroxyl group and a lipophilic phenyl group. Further, by virtue of its hydrophilicity (tetra), the sulfhydryl group on the surface of the ruthenium and the ruthenium oxide is strongly bonded by hydrogen bonding. Thereby, the polarity of the surface of the oxidized stone coated by the first coating material is lower than the polarity of the surface of the oxidized ash, and the adhesion between the oxygen etch and the second covering material can be easily used. The second covering material is coated. Further, the viscosity of the resin __ is lower than that of the resin such as _lipid. Therefore, the coating treatment of the oxidation 7 is easily performed by diluting the mash. Further, in the resin-coated cerium oxide of the present invention, at least one of a self-hardening resin, that is, a (B) resol type phenol resin, or (A) a novolak type phenol resin and a curing agent is further used. The second covering material is covered. For example, since the ruthenium oxide has a coating layer using the first and second covering materials, the viscosity is reduced by 16 when kneading with the rubber, so that the oxidation &5; reading rubber kinetics is improved, and it is considered that the coating layer is nonpolar or polar. Low rubber 27 201235392 Affinity improvement 'increased the dispersion of oxidation 7 in the rubber, by reducing the lunar month. The rotational resistance of the car and the improvement of the fuel consumption rate of the car and the driving stability are both excellent. Further, when the vulcanization operation is performed on the rubber composition, the second coating material is subjected to a hardening reaction with the first coating material, and the first coating material and the second coating material are co-formed to form a resin coating layer which is densely bonded to the oxide material. . Further, the second covering material, the rubber and the reinforcing resin blended as necessary are also hardened and integrated. It is considered that by such an action, sufficient hardness can be imparted to the vulcanized rubber composition. The resin-coated cerium oxide of the present invention is as described above, and its production is easy. Further, the vulcanized rubber composition coated with the resin-coated cerium oxide of the present invention has the same degree of breaking strength as the hardness of the vulcanized rubber composition coated with the oxidized cerium oxide of the present invention. As a sufficient strength of rubber products. As described above, by using the resin-coated oxidized oxide of the present invention as a tire raw material, it is possible to provide a tire that satisfies both environmental and stability properties. [Examples] Hereinafter, the present invention will be specifically described by way of Examples, but is not limited thereto. ~ &lt;Evaluation&gt; In the present Example, the kneading property of the unvulcanized rubber composition was evaluated by the following method. Further, the storage elastic modulus, loss tangent (addition), hardness, and breaking strength of the vulcanized rubber composition were measured by the following methods. 28 201235392 [Kneading] For the unvulcanized rubber composition, the relationship between torque and time (torque-time curve) is measured at 15 °C by using a hardened viscoelasticity tester (manufactured by CuiLASTOMETER MODEL III). After the rubber composition is melted, the minimum viscoelastic viscoelastic torque (N.m.) before vulcanization is determined to valence the kneading. The smaller the value of the hardened viscoelastic minimum torque, the better the kneading property. [Storage elastic modulus, loss tangent (tan 3)] For the vulcanized rubber composition, the number of vibrations was 1 〇 112 and 7 各自, respectively, using DMS 110' manufactured by SSI·NanoTechnology Co., Ltd. (: storage elastic modulus and loss tangent (tan &lt;5) 越高 The higher the storage elastic modulus, the better the driving stability of the automobile when the tire is made. The smaller the value of tan6 is, the smaller the rotational resistance of the tire is. [Hardness] For the vulcanized rubber composition, the hardness (Sh〇re a) was measured in accordance with JIS K6253 using a type A rubber hardness meter GS_7i9G manufactured by Teclock. The higher the measured value of the hardness, the more excellent the effect of imparting hardness. [Fracture Strength] For the vulcanized rubber composition, the breaking strength (MPa) of the test piece prepared as the matte No. 3 was measured in accordance with "TIS K6251" using STROGRAPH V10-C manufactured by Toyo Seiki Co., Ltd. The higher the breaking strength, the better the strength. &lt;Material used for surface treatment of cerium oxide&gt; oxidized stone cerium (a). ULTRASIL VN3 (trade name, manufactured by Degussa), 29 201235392 The nitrogen adsorption specific surface area measured by the BET method is 205 m 2 /g. Wet oxidized oxide eve. Cerium oxide (b): Zeosil 1115MP (trade name, manufactured by Rhodia Co., Ltd.), wet oxidized rock surface having a nitrogen adsorption specific surface area of 115 m 2 /g as measured by the BET method. O-nonylphenol: ORTHOCRESOL (trade name, manufactured by Nippon Steel Chemical Co., Ltd.). Cashew age: CARDANOL (trade name, manufactured by Golden Cashew products pvt. Ltd.). The decane coupling agent (1): 3-aminopropyltriethoxydecane KBE-903 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). Novolac type phenol resin (1): 50% by mass of a sterol solution of PS-6230 (trade name, manufactured by Qunjin Chemical Industry Co., Ltd.; cardanol-phenol-formaldehyde resin, softening point 85 ° C). Novolac type phenol resin (2): 50% by mass methanol solution of PSK-2320 (trade name, manufactured by Qunjin Chemical Industry Co., Ltd.; phenol-formaldehyde resin, softening point: 90 ° C). Hardener (1): 10 mass of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical Co., Ltd.). / 〇 water solution. Hardener (2): 10% by mass methanol solution of 4,4'-diaminodiphenylmethane, SUMICUREM (trade name, manufactured by Sumitomo Chemical Co., Ltd.). Resole type phenol resin: PL-6507 (trade name, manufactured by Kyoei Chemical Industry Co., Ltd.; cardanol-phenol-formaldehyde resin, a methanol solution having a solid content of 50% by mass). Decane coupling agent (2): bis(triethoxydecylpropyl)tetrasulfide 30 201235392 A 50% by mass decyl alcohol solution of ΚΒΕ-846 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.). &lt;Materials used in the production of the rubber composition&gt; Cerium oxide (al) to (a9): Surface-treated cerium oxide treated in the surface of Examples 1 to 5, 7 and 8 and Comparative Examples 1 and 2. Cerium oxide (M): Surface treated cerium oxide of Example 6. Natural rubber: RSS No. 3 Wax: SANOC Wax (trade name, manufactured by Ouchi Shinko Chemical Co., Ltd.). Oil: Diana Process AH40 (trade name, manufactured by Idemitsu Kosan Co., Ltd.). Antioxidant: Noclac 6C (trade name, manufactured by Ouchi Shinko Chemical Co., Ltd.). Stearic acid: Stearic acid SAKURA (trade name, manufactured by Nippon Oil Co., Ltd.). Remarks: Zinc Oxide (manufactured by Dai Chemical Co., Ltd.). Novolac type phenol resin (3): PS-4569 (trade name, manufactured by Qunrong Chemical Industry Co., Ltd.; for example, modified phenol-formaldehyde resin, melting point: 72 ° C). Sulfur: sulfur (manufactured by Tsurumi Chemical Industry Co., Ltd.). Hardener (1): 10% by mass aqueous solution of hexamethylenetetramine (manufactured by Mitsubishi Gas Chemical Co., Ltd.). Vulcanization accelerator: Nocceler-NS-P (trade name, manufactured by Ouchi Shinko Chemical Co., Ltd.). &lt;Surface treatment of cerium oxide&gt; According to the composition shown in Table 1, each material was stirred and mixed to prepare a surface-treated oxidized stone. In Table 1, the blending amount of each material is relative to 100 parts by mass of the oxide 31 201235392, and the amount of the material itself (the amount of the solution when the above material is a solution). (Example 1) In 100 parts by mass of oxidized stone (4), 27 parts by mass of cashew nut was added and used: she was stirred and mixed. Subsequently, by adding 126 parts by mass of phenolic/lunar-type resin (1) (5 〇 mass% methanol solution) and 9.0 parts by mass of hardener (1) (10% by mass aqueous solution), sand mixed, and using a hot air dryer at 9 The surface was treated with cerium oxide (al) by drying at 〇 ° C for 1 hour. (Example 2) In a enamel-packed oxidized stone eve (4), 45 parts by mass of o-methyl was added and mixed using a Scherr-mixer. Subsequently, the mixture was stirred and stirred by adding 9. G mass of the secret varnish type resin (1) (50 mass% methanol solution) and 9 Gf parts of the hardener (1) 〇〇 mass % aqueous solution, and using a hot air dryer at 9 〇 C It was dried for 1 hour to obtain a surface-treated cerium oxide (a2). (Example 3) In 100 parts by mass of the oxidized stone (4), 45 parts by mass of cashew nuts were added and mixed with a mixture of Scherrer. Subsequently, the mixture was stirred and stirred by adding a 9 Gf amount of a secret varnish type phenol resin (2) (50 mass% methanol solution) and 9 parts by mass of a hardener (1) (10 mass% aqueous solution), and using a hot air dryer. 9 〇C was dried for 1 hour to obtain a surface treated oxidized stone (μ). (Example 4) In 100 parts by mass of oxidized stone (4), 27 parts by mass of cashew nut was added and mixed with a Scherr mixer. Subsequently, the mixture was dispensed by adding 126f parts of a soluble y-type resin (50% by mass methanol solution), and the surface was treated with a hot air 32 201235392 dryer at 9 G ° C to obtain a surface treated oxidized handsome 4 ). (Example 5) In 100 parts by mass of the oxidized stone (4), 2 parts by mass of the sulphur coupling agent (1) and 1.5 mass of the cardanol were added and stirred and mixed using a Schneider mixer. Subsequently, the mixture was stirred and stirred by adding 3.0 parts by mass of the novolak-type phenol resin (1) (5 〇 mass% methanol solution) and 3.0 parts by mass of the hardener (1) (10% by mass aqueous solution), and using a hot air dryer to the thief (four) 丨The surface treated oxidized stone eve (a5) is obtained in an hour. (Example 6) Surface-treated cerium oxide (Μ) was obtained in the same manner as in Example 5 except that cerium oxide (a) was changed to cerium oxide (b). (Example 7) In one part by mass of cerium oxide (a), 2. 〇 part by mass of decane coupling agent (1) 4.5 i i injured cashew nut and 4.5 parts by mass of hardener (丨) (丨〇% by mass aqueous solution) And mix and mix using a Scherrer mixer. Subsequently, by mixing 9 parts by mass of the novolac type phenol resin (1) (50% by mass methanol solution) and 45 parts by mass of the hardener (1) (10 mass% / hydrazine aqueous solution), the mixture was mixed and dried by hot air. The machine was dried at 90 C for 1 hour to obtain a surface treated oxidized stone. (Example 8) To a mass of cerium oxide (a), 2 parts by mass of a decane coupling agent (1) and 4.5 parts by mass of cardanol were added and stirred and mixed using a Schneider mixer. Subsequently, by adding 9.0 mass-age awake varnish type resin (1) (5 〇 mass% methanol solution), 4.5 parts by mass of hardener (1) (1 〇 mass% aqueous solution) and 45 parts by mass of hardener (2) (10 mass% methanol solution) was mixed and mixed, and dried by hot air dryer 33 201235392 at 90 ° C for 1 hour to obtain surface-treated cerium oxide (a 7). (Comparative Example 1) In 100 parts by mass of the oxidized stone (a), 16.0 parts by mass of the sulphur coupling agent (2) (50% by mass of a decyl alcohol solution) was added and stirred and mixed using a Schneider mixer and dried by hot air. The machine was dried at 130 ° C for 1 hour to obtain a surface-treated oxidized oxide (a8) 〇 (Comparative Example 2). In 100 parts by mass of cerium oxide (a), 2.0 parts by mass of a decane coupling agent (1) and 20.0 parts by mass were added. A novolac type phenol resin (2) (50% by mass of a decyl alcohol solution) was stirred and mixed using a Schneider mixer and dried at 90 ° C for 1 hour using a hot air dryer to obtain a surface-treated cerium oxide (a9). 34 201235392 Comparative Example CN ο t-Η Ο (Ν 20.0 Ο 16.0 Example 00 ο ^•Η in inch · Ο (Ν — 卜ο r-Η ^ί· Ο oi ο VO Ο ο (Ν ο ΓΟ o rn Ο r—H 〇Ο &lt;Ν ο rn or〇 inchΟ oioi 12.6 cn ο — 〇〇\ o Os CN 100 inch · Ο ΟΝ o Ο τ—Η 卜CN 12.6 o 〇 矽 矽 (a) (mass) 矽 (b) ) (parts by mass) o-nonylphenol cardanol spleen coupling agent (1) hardener (1) novolac type phenol resin (1) ΐΓ Λ irA*· »-ilc 11 Λ IX t rlU&gt; \ hardener (1 Hardener (2) Solvent novolac type phenol resin decane coupling agent (1) decane coupling agent (2) Novolac type phenol resin (2) First covering material (parts by mass) Second covering material (parts by mass) Previous method (mass) 35 201235392 &lt;Production of Rubber Composition&gt; According to the composition shown in Table 2, each material was kneaded to prepare an unvulcanized rubber composition. λ, the unvulcanized rubber composition is heated in a mold to obtain a vulcanized rubber composition. In Table 2, the amount of the respective materials is relative to 1 part by mass of the natural rubber, and the amount of the material itself is shown (the amount of the solution when the above material is a solution). (Example 9) 100 parts by mass of natural rubber, 85 parts by mass of oxidized stone (al), 2 parts by mass of hydrazine, 4 masses of oil, 2 parts by weight of antioxidant, 4 parts by mass of stearic acid, and 5 parts by mass of zinc White, 10 parts by mass of the novolac type phenol resin (3), kneaded at 150 C for 5 minutes using a pressure kneader. To the obtained kneaded product, 25 parts by mass of sulfur, 5 parts by mass of a curing agent (1) (10% by mass aqueous solution), and 15 parts by mass of a vulcanization accelerator were added and kneaded at 90 ° C for 5 minutes using a twin-axis roll machine to obtain A flaky unvulcanized rubber composition. Subsequently, by adding the obtained rubber composition, to 15〇111111&gt;&lt; A 150 mm x 2 mm mold was heated at 15 Torr to obtain a vulcanized rubber composition. (Examples 10 to 16 and Comparative Examples 3 to 4) Except that each of cerium oxide (a1) was changed to (a2) to (a5), (b1), (a6) to (a9), and Example 9 The unvulcanized rubber composition and the vulcanized rubber composition obtained in the same manner. The hardened viscoelastic minimum torque, tan (5, hardness, and breaking strength) of each of the unvulcanized rubber compositions were determined by the method of the above evaluation. The results are shown in Table 2. 36 201235392 [3] &lt;] magnetic inch in oo 〇 &lt;Ν (N inch o IT) (Ν ir&gt;v£&gt; • n 〇 ΓΛ CN in 0.0290 VO oo 00 m l〇 oo o &lt;Ν inch (N inch iTi o in CN *&quot;Ή卜o 〇\ in 卜 00 (Ν Ο ο ο 00 00 (Ν Ο ΐ&quot;~Η Ό ΙΤϊ oo o &lt;Ν '· (N inch iTi o m (N ir&gt;«r&gt; •丨_ g o »*·· in ρ ο ο 5; SO &lt;Ν in νπ 00 o &lt;Ν inch (N inch iTi o ^T) (N gos »ri 5〇(Ν Ο ο VO gm (Ν 1—* inch 00 o CN inch inch inch κη o (N Ψ·^ o (N vn r- » S ο ο σί 00 ίΝ rn ιτ» 〇〇o CS inch CN inch &lt;n o m (N &lt;n 呀 o CN VO S ο νο αί 00 »—μ (N ί〇 00 o r—^ &lt;Ν inch (N rt o m &lt;N in FM F—H o 3 in ο 00 CN Ο ο 卜 (Ν ΟΝ ΟΝ Ο ••Η 00 o (Ν inch (N 寸 mo irj (N CM o CN S ο m ύ ^ί; ρ— ^ β Ο vr&gt; 00 o »—H CN inch inch inch κη o (N un in ΓΛ · · kri S ο ο 窆ο oi m 00 o (Ν inch OJ inch &lt;〇 o &lt;r&gt; (N to &lt;no irl νο S ο νο σί 00 Τ—Η (Ν /—Ν _ face ί 'w^ § /—N Take t〇H face ί (Ν' /—s _ ms V _ ? S—✓ 〇3 /—V _ tK m cd s^ liSf /—v Take φή ®1IIC A3 /—Ν _ face Ν Ν—✓ G&quot; cd _ object K -O /—N take m 00 s A3 /—N _ oT λ i _ vK i _ face ί ¥ i iM 轫c 、,〆/—S take φ| W control/«—V take φ| «3 iim ας tfh iwi _ Sw^ Aim 洛·| ί fx 汹Aim 衾寒 i Φ4 i φ| tK I i W im Nw/ 藏 f/ 〇J i δ 七±1 卿1? 〇4 1 ^Lm ίε JS ¥ ^ο 1? α. S 缌37 201235392 From the results of Table 2 Compared with the unvulcanized rubber compositions of Comparative Examples 3 and 4, since the rubber composition of the unvulcanized rubber composition of Examples 9 to 16 is melted, the value of the minimum value of the hardened viscoelasticity to vulcanization is small, so that rubber is produced. Further, the kneading rubber composition of Comparative Examples 3 and 4 was found to be higher than the vulcanized rubber compositions of Comparative Examples 3 and 4, since the vulcanized rubber compositions of Examples 9 to 16 had higher storage elastic modulus values and tan (5 Smaller value's excellent driving stability and reduced tire turnover The fuel consumption rate improvement effect of the automobile with high resistance is also high. Moreover, it is known that the vulcanized rubber composition of Comparative Examples 3 and 4 has a higher hardness than the vulcanized rubber composition of Examples 9 to 16, so the embodiment The surface-treated cerium oxide (resin-coated cerium oxide) of 1 to 8 is excellent in hardness, and the vulcanized rubber compositions of Examples 9 to 16 have fractures equal to or higher than those of the vulcanized rubber compositions of Comparative Examples 3 and 4. According to the present invention, it is possible to provide a resin-coated oxidized stone which is excellent in kneadability with rubber and excellent in hardness. According to the present invention, it is possible to provide a rubber composition and a tire which have both improved fuel consumption rate and driving stability of the automobile by reducing the rotational resistance of the tire. [Simple description of the figure 3 (none) [Description of main component symbols] (none) 38

Claims (1)

201235392 VII. Patent application scope: 1. A resin-coated cerium oxide, which is a cerium oxide having a nitrogen adsorption specific surface area of 50 to 300 m 2 /g as measured by the BET method, sequentially using the first covering material and the second The covering material is characterized in that: the first covering material contains a brewing material; and the second covering material contains (A) a novolak type phenol resin and a curing agent, and (B) a resol type phenol At least one of the resins. 2. The resin-coated cerium oxide according to the first aspect of the patent application, wherein the first covering material contains a hardener. 3. The resin-coated cerium oxide according to claim 1 or 2, wherein the first covering material contains a decane coupling agent. A rubber composition comprising a oxidized granule and a rubber coated with a resin as in the first aspect of the patent application. 5. A type of tire which is used in a tire tread portion as in the fourth aspect of the patent application. 39 201235392 IV. Designation of Representative Representatives: (1) The representative representative of the case is: ( ). (None) (2) A brief description of the symbol of the representative figure: 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: