TWI352718B - - Google Patents

Description

IX. Description of the Invention: [Technical Fields of the Invention] The present invention relates to a rubber composition which is excellent in physical properties and rubber physical properties of an unvulcanized rubber. Further, the present invention relates to a rubber article obtained from the rubber composition. C. Prior Art 3, the main use of stone black is used as a filler for rubber compositions for tires. In recent years, in order to meet the requirements of low fuel consumption in the automotive industry, a part of carbon black is being reviewed and replaced with a cerium oxide-based filler, particularly cerium oxide. However, the rubber composition of carbon black and cerium oxide is used, and the viscosity of the rubber composition which is only blended with carbon black is higher than that of the un-vulcanized rubber (2), and the cohesiveness of the sulphur dioxide is not easily dispersed. (3) Since the Moisturizer has a high Mohs hardness, there is a problem that the wear of the processing machine such as a rubber mixer or a molding machine is severe. Furthermore, in combination with the composition of carbon black and cerium oxide, in order to express the characteristics of the tire which can compete with the rubber composition which only blends with carbon black, it is necessary to use the two emulsified stone and the south price of the smashing and coupling agent to cause cost. The problem. In order to solve the above problems, a method of blending a polymer composition with a filler such as calcium carbonate has been proposed (see Japanese Laid-Open Patent Publication No. Hei 09-269307, No. Hei 09-194634, No. Hei 09-077915, Japanese Laid-Open Patent Publication No. Hei 09-150606, No. Hei 10-087896. Calcium carbonate is widely used as a rubber extender, reinforcing agent, etc., and the rubber composition blended with calcium carbonate has a low viscosity in an unvulcanized state, and has a roll wrap compared to a rubber composition in which cerium oxide is blended. The advantages of good volume. Further, since the pH of calcium carbonate is weakly alkaline, the rubber composition blended with calcium carbonate has an advantage of no vulcanization inhibition. However, once calcium carbonate is blended in a large amount in the rubber composition, the mechanical properties of the rubber composition are deteriorated. SUMMARY OF THE INVENTION The main object of the present invention is to obtain a rubber composition excellent in both unvulcanized rubber physical properties and vulcanized rubber knee properties. As a result of intensive review in order to solve the above problems, the present inventors have selected carbonaceous materials and/or oxime, oxygen cut, and modified carbonic acid having a specific structure for a predetermined amount in a rubber selected from at least one of natural rubber and synthetic rubber. The obtained rubber composition was found to have desired physical properties, and the present invention was completed by further focusing on the review. That is, the present invention relates to the following rubber compositions and rubber products. Item 1. A rubber composition comprising, as a rubber component selected from the group consisting of at least 2 rubbers and synthetic rubbers, comprising the following ingredients 2: Component 1: 20 to 100 parts by weight selected from the group consisting of In any one of (1) to (3) consisting of (1) carbon black (7) carbon dioxide, and (3) a mixture of carbon black and trioxane, component 2: 〇. 5 parts by weight or more~ Less than 20 parts by weight of a modified carbonate having a layer of a dioxide layer and a layer of a decane coupling agent. The second rubber composition is inclined to the edge component selected from at least one of d rubber and synthetic rubber. The rubber component comprises the following components 1 and 1352718 component 1: 20 to 100 parts by weight. Any one of (1) to (3) selected from the group consisting of (1) carbon black, (2) cerium oxide, and (3) a mixture of carbon black and cerium oxide, component 2: 0.5 parts by weight The above-mentioned to less than 20 parts by weight of the (1) cerium oxide layer and (ii) 5 are obtained by treating at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester. The organic acid layer and (iii) a modified carbonic acid having a layer of a decane coupling agent. A preferred aspect of the rubber composition is 100 parts by weight of a rubber selected from at least one of 10 natural rubber and synthetic rubber, comprising: component 1: 20 to 100 parts by weight of carbon black, and component 2: 0.5~ 18 parts by weight of the (i) cerium oxide layer, (ii) organically obtained by treating at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester An acid layer, and (iii) a modified calcium carbonate having a layer of a decane couple 15 mixture. Item 3. The rubber composition according to Item 1 or 2, wherein the component 1 is a mixture of (3) carbon black and cerium oxide, and the mixing ratio of carbon black: cerium oxide is 0.5 by weight: 99·5~99.5: 0.5. The rubber composition 20 according to any one of the preceding claims, wherein the component 1 is (2) cerium oxide, and the rubber composition further comprises the following component 3: component 3 The blending amount of the decane coupling agent with respect to cerium oxide is 0.1 to 30% by weight. A preferred aspect of the rubber composition is 100 parts by weight of a rubber selected from at least one of 7 1352718 'natural rubber and synthetic rubber, comprising: component 1: 20 to 80 parts by weight of a dioxide dioxide eve' ingredient 2 0.5 to 15 parts by weight of the (1) cerium oxide layer, (ii) obtained by treating at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester 5 The organic acid layer, and (iii) the modified calcium carbonate having a decane coupling agent layer, and the component 3: the decane coupling agent is added in an amount of 0.1 to 30% by weight based on the cerium oxide. The rubber composition according to any one of the items 1 to 3 wherein the component 1 is (3) a mixture of carbon black and cerium oxide, and the rubber composition further comprises the following components 3: Component 3: The blending amount of the decane coupling agent with respect to cerium oxide is 0.1 to 30% by weight. Item 6. A rubber article obtained by forming a rubber composition of any one of items 1 to 5 into a shape. The following is a detailed description of the invention. In addition, "%" and "parts" in this manual indicate "% by weight" and "parts by weight" unless otherwise stated. Rubber 20 A rubber selected from at least one of natural rubber and synthetic rubber is used as the rubber. Natural rubber is a rubber-like polymer material obtained from natural plants, and has a chemical structure of a 1,4-polyisobutylene structure, and the type thereof is not particularly limited. 8 1352718 ' The synthetic rubber can be obtained by using either a diene rubber or a non-diene rubber. Specifically, the synthetic rubber used may, for example, be a cis-1,4-polyisobutylene, an emulsion polymerization butadiene copolymer, a solution polymerization butadiene total 5 polymer, and a low cis-1,4-polybutadiene. , Gaoshun-1,4-polybutadiene, ethylene-propylene-diene copolymer, gas butadiene, halogenated butyl rubber, acrylonitrile-butadiene rubber, ethylene-propylene copolymer, butyl rubber, amino Ethyl formate rubber, polyoxyalkylene rubber, fluororubber, gas sulfonated polyethylene, chlorinated polyethylene, epoxy propylene rubber, acrylic rubber, acrylic acid 10 ethyl copolymer, ethylene vinyl acetate copolymer, nitrile rubber , hydrogenated nitrile rubber, epoxidized natural rubber, and the like. Among the above rubbers, natural rubber, cis-1, 4-polyisobutylene, emulsion polymerization butadiene copolymer, solution polymerization butadiene copolymer, low-cis-1, 4-polybutadiene, Gaoshun-1 , 4 - polybutadiene. 15 The rubber may be used alone or in combination of two or more kinds selected from natural rubber or synthetic rubber. The mixing ratio can be appropriately set in accordance with the required characteristics. Further, in order to improve workability and the like, an oil-extended rubber in which a stretching oil is blended in advance may be used for the above rubber. 20 Ingredient 1 The component 1 blended with the rubber composition of the present invention is any one of (1) carbon black alone, (2) cerium oxide alone, or (3) a mixture of carbon black and cerium oxide. The blending ratio of the component 1 to the rubber composition is 20 to 100 parts by weight based on 100 parts by weight of the rubber, and can be appropriately adjusted to obtain the desired physical properties of 9 1352718 '. Hereinafter, the case of (1) to (3) will be described. (1) Carbon black The carbon black used in the present invention can be used as a carbon black which is usually used as a rubber reinforcement. The BET specific surface area of the carbon black is not particularly limited, but a BET specific surface area according to the II gas adsorption method is preferably 2 〇 m 2 /g or more, preferably 20 to 22 〇 m 2 /g, and 20 to 200 m 2 . /g is better. When it is used in applications such as tire treads that require reinforcement, it is particularly suitable to use a BET specific surface area of 70 m2/g or more, preferably 7 〇 to 22 〇 m 2 /g, and 70 〜 200m2/g is better. When the BET specific surface area of the carbon black is in the above range, the dispersibility of carbon black is good, and a rubbery composition having excellent characteristics such as tensile properties, tensile strength, and abrasion resistance can be obtained. 15 When the component 1 is (1) carbon black alone, the blending amount of the carbon black is about 20 to 100 parts by weight with respect to 100 parts by weight of the rubber, and preferably about 4 to 9 parts by weight, and further 40. More preferably, it is 80 parts by weight. When the blending amount of the carbon black is in the above range, the Mooney viscosity is improved without lowering the workability, and a particularly excellent rubber composition such as abrasion resistance and tensile properties can be obtained. (2) Cerium oxide As the cerium oxide used in the present invention, it is usually used as a rubber for reinforcing the cerium. Specific examples of the cerium oxide include wet sulphur dioxide, dry cerium oxide, and the like. 10 The specific surface area of the beryllium dioxide is not particularly limited, but a BET specific surface area of the nitrogen adsorption method is preferably 2 〇 m 2 /g or more and 20 to 400 m 2 /g is preferable. 〇~300m2/g is better. When the BET specific surface area of the cerium oxide is in the above range, the dispersibility of the silica is good, and a rubber composition which is excellent in tensile properties, tensile strength, and abrasion resistance can be obtained. When the component 1 is (2) cerium oxide alone, the amount of cerium oxide blended is 20 to 100 parts by weight with respect to 100 parts by weight of the rubber, and preferably 4 Torr to 9 Å by weight, preferably 40 to 80 parts by weight. The parts by weight are more preferred. When the blending amount of the cerium oxide is within the above range, the Mooney viscosity is improved without lowering the workability, and a particularly excellent rubber composition such as abrasion resistance and tensile properties can be obtained. (3) Mixture of carbon black and cerium oxide (3) A mixture of carbon black and cerium oxide used in the present invention is obtained by mixing the above (1) carbon black and the above (2) dioxane by a known method. mixture. When the wound 1 is (3) black and sulfur dioxide, the mixing ratio of carbon black and silica dioxide is 〇5: 99 5~99 5 : 〇5, and 1 重量 by weight. : 9〇~9〇: 10 is better, with 3〇: 70~70: 30 is better. When the wound 1 is a mixture of (3) carbon black and oxygen dioxide 11, the blending amount of the component 1 is preferably 2 (M (8) parts by weight and preferably about -9 parts by weight with respect to the rubber of the portion. When the blending amount of the mixture is in the above range, the Mooney viscosity is improved without lowering the workability, and JL can obtain a particularly excellent rubber composition such as Μ wear resistance and 1352718 tensile property. Component 2: Modified calcium carbonate The rubber composition of the invention comprises the modified calcium carbonate as the component 2. The modified carbonated dance used in the present invention is a raw material of calcium carbonate to which a modified layer of carbon dioxide is attached to the second layer of the oxidized stone layer and the stone smelting coupling agent. Or a calcium dioxide layer adhered to the calcium carbonate as a raw material, and is selected from at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester. The organic acid layer and the modified layer of three layers of the decane coupling agent layer. Here, the so-called "layer" may be covered only with the raw material calcium carbonate or partially modified calcium carbonate (ie, having a selected from the group consisting of Bismuth layer, decane coupling agent All or a part of the surface of the layer and the organic acid layer or the partially modified calcium carbonate) does not need to continuously cover the entire surface. The structure of the surface of the modified calcium carbonate of the present invention may be (1) The order of the cerium oxide layer, the organic acid layer, and the layer of the coupling agent is from the inside to the outside, the -11 layer, the de-coupler layer in the order from the inside to the outside, and (3) the dioxide (4). The order of the organic acid layer is from the inner side to the outer piled portion, (4) the dioxygen (10) layer, the organic acid layer, and the Wei coupler layer are partially mixed (single layer). The thickness of each layer can be obtained by It is difficult to set it properly. • The raw material carbonic acid is used in the reformed carbon used in the present invention. The carbonic acid type of the raw material is not particularly limited, and a known carbonic acid can be used, for example, heavy carbonic acid feeding and synthesis (Shen 12 1352718). Degraded) Calcium carbonate, etc. Heavy calcium carbonate can be used to produce natural calcium carbonate rough by using a drum mill, a high-speed rotary grinder (impact shear grinder), a container-driven media grinder (ball mill), Agitating mill, planetary ball mill, 5 jet mill, etc. are pulverized by a known dry or wet pulverization method. Synthetic (dewatering) carbonate can be treated with lime milk-carbon dioxide reaction, gasification I bow A known method such as a soda ash reaction method, a lime milk-soda ash reaction method, etc. One example of a lime milk-carbon dioxide reaction method is a limestone rough 10 by coke or petroleum-based fuel (heavy or light oil), natural gas. , LPG, etc. are burned into quicklime, and then the quicklime is hydrated to form a hydrogenation dance slurry, and then reacted with carbon dioxide bubbles generated during combustion to obtain calcium carbonate. According to the conditions of the set carbon dioxide reaction, Obtaining the fine particles of the desired fine particle size. 15 Others can also be applied to the addition of a calcium hydroxide slurry by adding water to the zinc salt formed by the oxidation of the hydroxide, and simultaneously reacting with the carbon dioxide bubbles to produce the above. A method of calcium carbonate with finer calcium carbonate (Japanese Patent No. 401044). The BET specific surface area of the raw material calcium carbonate can be appropriately set, but it is usually 20 5 to 120 m 2 /g, and preferably about 20 to 110 m 2 /g, and more preferably about 50 to 10 μm 2 /g. When the BET specific surface area of the raw material calcium carbonate is too large, the amount of the fatty acid, the fatty acid salt, the fatty acid ester, the resin acid, the resin acid salt or the resin acid vinegar must be increased. Due to fatty acids, fatty acid salts, fatty acid esters, resin acids,

13 Tree laurate and resin acid are used as softeners, which may damage the rubber. On the other hand, if the BET specific surface area of the raw material carbon material is too small, the reinforcing effect of blending with the rubber ray may be lowered. The particle size of the raw material carbonate can be within the range of achieving the effect of the present invention, and the size of the original particle control of the raw material carbonic acid particles is 〇〇1~〇5. The mouth is preferably left and right, and is preferably about 0.02 to 0.4//m.

• cerium oxide layer The oxidized stone layer is treated with a layer of oxidized 7 aqueous sol. 2 10 One of the oxidized Xishui wins, the oxidized stone eve can be quantitatively attached to the carbonic acid mother. The dioxo-hydrated sol can be produced by a known method, and for example, a cerium oxide hydrosol obtained by an acidic decomposition method can be used. Further, it is also possible to use an inorganic acid such as hydrochloric acid or sulfuric acid, an organic acid such as sulfuric acid or acrylic acid, or an acidic substance such as carbon dioxide or sulfur dioxide, which is added to the solution of the sodium sulphate solution. Crystalline dioxide dioxide hydrosol. Alternatively, a cerium oxide hydrosol produced by a dialysis method produced by passing sodium sulphate through a semipermeable membrane may be used. Further, a dihydrate 11 hydrosol produced by an ion exchange method using the ion exchange tree 1 can also be used. 2, for example, adding an appropriate concentration of the aqueous solution to the carbonic acid cracking solution, and the acidic substance such as inorganic acid or organic acid is dripped on the surface of the surface, and the activated carbon dioxide is treated by the active sulfur dioxide. The surface method is exemplified as a method of treating calcium carbonate in a cerium oxide hydrosol. Further, a method of treating the surface of the calcium carbonate by adding the previously prepared cerium oxide hydrosol to the acid-reducing liquid reduction liquid 14 and vigorously stirring it may be used. The concentration of the solid component of the carbonated mother's slurry which can be suitably used (carbonic acid: the degree of suffering) is from 0.5 to 20%, and more preferably from about 1 to about m. Further, the amount of the dioxide in the aqueous solution of the sodium sulphate can be suitably used. The concentration around. The amount of cerium oxide deposited on the calcium carbonate may be adjusted according to the BET specific surface area of the calcium carbonate, and is usually about 5% to 15 parts by weight for the carbonic acid of the (10) parts by weight of the raw material. Further, it is preferably 12 parts by weight, more preferably 2 to 10 parts by weight. When the amount of cerium oxide adhered to the calcium carbonate by the cerium oxide water lanthanum sol, the amount of cerium oxide is obtained by the cerium dioxide adhered to the cerium carbonate. When the amount of cerium oxide relative to calcium carbonate is too small, the reaction site of the cerium oxide coupling agent to be described later is reduced, and the desired rubber physical properties may not be exhibited. On the other hand, when the amount of the dioxide is too large, since the remaining cerium oxide hydrosol is present in the solution except for the 15 attached to the surface of the calcium carbonate, the cerium oxide hydrosol can make the calcium carbonate strong when dry. The solidification of the ground increases the coarse particles that are difficult to break. A calcium carbonate filler containing such coarse particles may lower the tensile strength, flex crack resistance, and the like of the rubber composition. 20 Organic acid layer The organic acid layer is a layer obtained by treating at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester. The fatty acid used in the present invention is exemplified by a saturated or unsaturated fatty acid having a carbon number of from 6 to 24, particularly 15 being from 1 to 20. The saturated or unsaturated fatty acid having a carbon number of about 6 to 24 may, for example, be stearic acid, palmitic acid, lauric acid, behenic acid, oleic acid, fenic acid or linoleic acid. In particular, stearic acid, palmitic acid, lauric acid, and oleic acid are preferred, and two or more of them may be used in combination. Examples of the salt of the fatty acid include an alkali metal salt such as a sodium salt or a potassium salt of a saturated or unsaturated fatty acid having a carbon number of from 6 to 24, particularly from 1 to 20, as an example. Further, examples of the fatty acid ester include a saturated or unsaturated fatty acid having a carbon number of about 6 to 24, particularly 10 to 20, and a hydrogen having a carbon number of about 6 to 18, each of which is particularly saturated with a carbon number of 10 to 18. An example of an aliphatic ethanol vinegar or the like. Examples of the resin acid, the resin acid salt, and the resin acid used in the present invention include rosin acids such as rosin acid, deuterated rosin acid, and dihydroabietic acid, or polymers thereof, disproportionate rosin, hydrogenated rosin, and polymerization. Rosin, or a salt thereof (for example, an alkali metal salt, an alkaline earth metal salt) or an ester (for example, quaternary tetraalcohol, ester, glycerin, hydrogenated rosin methyl ester, triethylene glycol, vinegar, quaternary tetraol, Ester) and the like. Among them, rosin acid and dehydroabietic acid are preferred. In the treatment method of the carbonate of the fatty acid 'fatty acid salt and/or the fatty acid ester, a method of saponification as follows is exemplified. First, the fatty acid is heated in an alkali metal aqueous solution such as a NaOH aqueous solution or a KOH aqueous solution to be saponified (to be a metal salt such as a Na salt or a K salt) to form a solution. Here, the concentration of the aqueous alkali metal solution is about 6%, and preferably about Mo%. The amount of the aqueous alkali metal solution is not particularly limited as long as it is required to saponify the fatty acid. 1352718 Next, the suspension of calcium carbonate forming the cerium oxide layer is preheated to 30 to 50 C′, and then the above-mentioned solution fatty acid soap is added to the suspension and stirred and mixed to form a fatty acid containing / or organic acid layer of fatty acid salts. The addition ratio of the fatty acid soap to the aqueous suspension of calcium carbonate is about 〇~70%, and preferably about 1 〇~50%. The method of using the soap of the fatty acid Na or the like as it is is prepared by previously preparing the heated aqueous solution and treating it in the same manner as above. • You can also use a method that does not saponify fatty acids. For example, calcium carbonate which forms a ceria layer can be stirred while being heated to a melting point of 10 fatty acids in a powder state, and a fatty acid is added thereto, and a fatty acid layer is formed by mixing and mixing. The method of treating a resin acid, a resin acid salt, and/or a resin acid ester can be carried out in the same manner as the above fatty acid, fatty acid salt and/or fatty acid ester. Specifically, the resin acid is heated in an alkali metal 15 aqueous solution such as a NaOH aqueous solution or a KOH aqueous solution, and is saponified (to become a metal φ salt such as a Na salt or a K salt) to form a solution. The concentration of the aqueous alkali metal solution is about 1 to 40%, preferably about 1 to 20%, and the amount of the aqueous alkali metal solution is not particularly limited as long as the amount of the resin acid is saponified. Next, the suspension of the calcium carbonate layer in which the cerium oxide layer has been formed is preheated by 20 to 30 to 50 ° C, and then the solution-like resin acid fertilizer is added to the suspension, and the mixture is mixed and mixed. It is formed into an organic warm layer containing a resin acid and/or a resin acid salt. The addition ratio of the resin acid soap to the aqueous suspension of carbon_ is about 10 to 70%, preferably about 1 to 5 %. The method of using the fat (4) postal soap as it is is prepared in advance.

17 1352718 _ An aqueous solution of the heated resin acid soap is treated in the same manner as described above. Further, a method of treating the resin acid without saponifying it may be employed. For example, the calcium carbonate forming the cerium oxide layer may be stirred while being heated to a temperature equal to or higher than the melting point of the resin acid, and a resin acid may be added thereto to form an organic acid layer containing a resin acid by stirring and mixing. The amount of the organic acid layer, that is, the amount of adhesion selected from at least one of a group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester, can achieve the effect of the present invention. The amount is usually 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight, and more preferably 2 to 12 parts by weight, based on 100 parts by weight of the raw material. • Decane coupler layer The decane coupler layer is a layer obtained by treatment with a decane coupling agent. The decane coupling agent used in the present invention may, for example, be vinyl helium 15 , vinyl trimethoxy decane, ethylene triethoxy decane or vinyl tri (cold monomethoxy ethoxy) decane. , (1,4,1,epoxycyclohexyl)ethyltrimethoxy decane, (2-aziridine)aminopropyltrimethoxydecane, 7-glycidoxypropyltrimethoxy decane , 7-glycidoxypropyltrimethyldiethoxylate, 7-glycidoxypropyltriethoxylate, 2〇r-methylpropenylpropylmercaptofluorene Oxydecane, r-methacryl propyl trimethoxy decane, 7-methacryl propyl decyl diethoxy decane, decyl propylene propyl triethoxy decane ' Ν - yS (nitrogen Propyl ring)r-aminopropyl decyl dimethoxy decane, N-/3 (azepine) τ-aminopropyltrimethoxy sylvestre, N- yS (aziridine) τ-aminopropyl three Ethoxy Brothel, 3 18 1352718 .•-Aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, N-phenyl-r-aminopropyltrimethoxydecane, 7-Gas-propyl Trimethoxy hydrazine , r-hydrothiopropyltrimethoxy zeoxime, di-(3-[triethoxy oxalyl]-propyl)-tetrasulfide (TESPT), di-(3-[triethoxy] Decane-·5 base]-propyl)~disulfide. Among them, r-(2-aziridine)aminopropyltrimethoxy decane, 3-aminopropyltriethoxydecane, N-nitrogen (aziridine)-aminopropyldimethoxy sulphide are especially used. Xishou, γ-虱 thiopropyltrimethoxy oxalate, bis-(3- ethoxy ethoxy)-propyl)-tetrasulfide, di-(3 -[triethoxy shixi 10 Alkyl]-propyl)-disulfide is preferred. The method of treating the calcium carbonate using a decane coupling agent is not particularly limited, and various methods known hitherto can be used. For example, when the calcium carbonate formed with the cerium oxide layer and the organic acid layer is a dry powder, the surface can be mixed with the carbon dioxide at the end of the sanding machine to drip the stone singer 5 «agent' or by using the spray (four), etc. Spray, and make the Wei coupling layer on the surface of the carbonate. At this time, it can also be «heated and dried after treatment in Table©. Further, calcium carbonate having a ruthenium oxide layer and an organic acid layer is formed as a suspension. When the state is #, a water-soluble Wei coupling agent is put into the suspension, so that the Shixi sinter coupling agent is attached to the surface of the carbonated dance surface. After the treatment, and finally, the mixture is filtered and dried, so that the Wei couple can be attached to the carbonic acid touch and the treated carbonic acid is about a suspension. In order to make the treatment uniform, a mixer or a bead mill can be used. Wet grinder for machine and sand mill. The amount of adhesion of the smouldering agent can be determined according to the bet ratio of the carbonated carbonate

19 1352718 • The area and the like are appropriately adjusted, and the amount of calcium carbonate relative to 100 parts by weight of the raw material is usually about 0.05 to 1 part by weight, and preferably about 0.07 to 5 parts by weight, and is 0 to 1 to 3 parts by weight. The difference is better. • Modified Calcium Carbonate 5 One of the modified calcium carbonates of the present invention is a modified calcium carbonate having two layers of (1) a cerium oxide layer and (ii) a decane coupling agent layer. The modified calcium carbonate having the (i) cerium oxide layer and the (i oxane coupling agent layer) can be produced by treating the above-mentioned cerium oxide hydrosol and treating the broth coupling agent with calcium carbonate as a raw material. The other one of the modified calcium carbonate of the present invention has (1) a cerium oxide layer, and (11) is selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester. At least one of the three layers of the organic acid layer treated in the group, and (iii) the fine alkane coupling agent layer is modified.

A modified calcium carbonate having three layers of (1) a cerium oxide layer, a (cerium) organic acid layer, and ((1) a decane coupling agent layer 15, for example, (a) may be dissolved in the calcium carbonate by the above-mentioned silica dioxide Treatment of Sheng, treatment of organic acids, and treatment of Shi Xi Shao coupling agent. Further, (b) each of the modified carbon gorge and the (II) organic acid layer having a (1) dioxygenated layer and a (9) organic acid layer may be blended in a rubber composition and mixed and produced in a rubber composition. In the case of _, it is also possible to add a three-purpose blend of Shishi sinter coupling agent as a part of the component 3. Specifically, the manufacturing method of (5) (4) is exemplified by a method having the following steps (1) to (4). And adding at least one selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin resin, a resin acid salt, and a resin acid ester to the original 20 (2), and having the carbonic acid layer of the cerium oxide layer a step of forming an organic acid layer in the calcium slurry; (3) a step of dehydrating and drying the calcium carbonate slurry forming the cerium oxide layer and the organic acid layer; (4) the obtained calcium carbonate particles are carried out by using a decane coupling agent The step of surface treatment to form a layer of decane coupling agent. The modified calcium carbonate of (1) a cerium oxide layer, (ii) an organic acid layer, and (iii) a decane coupling agent layer can be formed on the raw material calcium carbonate by the aforementioned method. On the other hand, specifically, the method (b) may be a method of adding a partially modified calcium carbonate having a (1) cerium oxide layer and (ii) an organic acid layer to a rubber, and then adding a decane coupling agent to the rubber, followed by adding a decane coupling agent to the rubber. A method of mixing is also taken as an example. Further, another example is a method in which a decane coupling agent is added to a rubber, and then a portion of the modified calcium carbonate having the (1) cerium oxide layer and the (ii) organic acid layer is added to the rubber and mixed. Partially modified calcium carbonate and shixi shuang coupler having ruthenium dioxide layer and (1)) organic acid layer are respectively added to rubber, and then mixed with (1) dioxygen layer and (9) organic by mixing The acid layer partially reforms the surface Ji of the carbonic acid #5 to form a three-layered layer of (1) a disulfide layer and (9) an organic acid layer and (4) a stone layer of the #1 layer. The amount of Shi Xixuan coupling #1 with the (·) oxidized stone layer and (ii) the organic acid layer partially modified carbonated mother and the Shixi smelting coupling (4) combined with the formation of the Wei coupling agent layer when the group is transferred The weight of the raw material carbonic acid is about 0.05 to 10 parts by weight, and the total weight of the core is preferably about 0.1 to 3 parts by weight. The BET specific surface area of the modified calcium carbonate can be appropriately set within the effect of achieving the present invention and is usually about 4 to 110 m 2 /g, and 15 to 100 m 2 /g & right is preferred ' and 40 to 90 m 2 /g. The left and right are better. When the modified BET specific surface area of calcium carbonate is too large, the reinforcing effect on the rubber may be impaired. On the other hand, if the BET specific surface area of the modified calcium carbonate is too small, the reinforcing effect when blended with rubber may be lowered. The particle size of the modified calcium carbonate can be appropriately set for the purpose of obtaining the desired effect, and the original particle control of the modified calcium carbonate particles in the scanning electron microscopy is usually 0.01 to 〇 _6 y m. Good, and 〇〇 2~0.5ym is better. Component 3: decane coupling agent When cerium oxide is blended as the component 1, it is preferred to incorporate the decane coupling agent as the component 3 in the rubber composition. When the cerium oxide and the decane coupling agent are blended together, the elastic modulus and the abrasion resistance of the rubber composition can be improved, and particularly when the rubber composition is used as the material to form the tire, the rolling resistance and the grip performance of the tire can be improved. The blending amount of the decane coupling agent to the rubber composition is about 0.25 to 30% by weight based on the amount of cerium oxide, and preferably about 1 to 2% by weight, and preferably 3 to 10% by weight. For better. Partially modified carbon strontium calcium and decane coupling agent having two layers of (1) cerium oxide layer and (ii) organic acid layer are individually added to the rubber, and the rubber layer is formed into a red layer of the towel. The amount of the coupling agent added to the rubber composition is about 1 to 35% by weight based on the amount of the second oxidation, and is (10) by weight. /. The left and right are better. Here, 1352718. The so-called cerium oxide blending amount is the total amount of the component 1 in the case where the component 1 is only cerium oxide, and the component 1 is the mixture of carbon black and cerium oxide. The component of the mixing ratio of phlegm. : The decane coupling agent which is the same as the oxime / 5 alkane coupling agent described in the surface treatment of the above modified calcium carbonate can be used. The blending form of the decane coupling agent is not particularly limited, and may be blended in a liquid form of a single substance having a purity of 1% by weight, or may be impregnated with a powder such as calcium carbonate or oxidized hair to be blended in the form of a composition. ##胶组成10 The rubber composition of the present invention contains a specific content of rubber component, component 1: blackened and/or sulphur dioxide, and component 2: modified carbonic acid, and used cerium oxide or two When the mixture of cerium oxide is used as a component, it further contains component 3: Shi Xi Xuan coupling agent. The rubber composition of the present invention may further contain a known substance if necessary. 15 Known substances include other fillers such as clay, aluminum hydroxide, light calcium carbonate, heavy calcium carbonate, naphthenic oil, paraffin oil, aromatic oil, etc. • oil, aging inhibitor, active agent, Stearic acid, zinc oxide, wax, and the like. Further, a vulcanizing agent such as a sulfur continuation or a vulcanization accelerator may be appropriately blended. The rubber composition of the present invention can be produced by mixing a rubber component in an ordinary manner, a component of 2, a component 2, a component 3 in a special case, and a binder thereof as necessary. When the rubber composition is produced, heating or extrusion may be appropriately performed. For various conditions of the mixing, for example, the type of the mixing device, the input volume, the rotational speed of the drum, the piston force, and the like, 23 1352718, the mixing temperature, and the mixing time can be appropriately set for the purpose. The breaking device is also not particularly limited and may be appropriately selected from known mixing devices for the rubber composition to be dropped. Specifically, you can use the Bangseli blender (Xinyi U-s trademark registration), Yingda secret machine 乂 5 5 a 'V eve only) (trademark registration), kneading machine, roller, etc. Use closed or open. Moreover, the conditions of heating and extrusion can also be set suitably. Further, the heating means and the extrusion means can be appropriately selected from known apparatuses. Hereinafter, the rubber group 1 of the present invention will be further described with reference to specific aspects. Layout 1: In comparison with the weight of 100 parts of the oak, there is a 1:2 (H1M parts by weight of black, ingredient 2: 0·5~18 will change the side of the base of calcium. In one aspect of the rubber composition of the present invention, for example, the aspect 1: phase 15 is blended in a specific amount with respect to 100 parts by weight of a rubber component selected from at least one of natural rubber and synthetic rubber. The carbon black of component 1 and the component 2 have (1) a cerium oxide layer, and (ii) is selected from the group consisting of a fatty acid, a fatty acid salt, a fatty acid ester, a resin acid, a resin acid salt, and a resin acid ester. A composition of the organic acid layer obtained by the treatment and the modified calcium carbonate of the (iii) decane coupling agent layer. The rubber composition of the aspect 1 may be a rubber selected from at least one of natural rubber and synthetic rubber. The carbon black is blended in a specific amount, and the modified calcium carbonate having the (i) SiO2 layer, (ii) the organic acid layer, and (iii) the decane coupling agent layer is then produced by folding. 24 1352718 • The order of addition (blending) of carbon black and modified calcium carbonate is not particularly limited, and it can also be blended and modified after blending carbon black. Calcium carbonate can also be blended with carbon black after blending modified carbonic acid, and can also be blended with carbon black and modified carbonic acid. The amount of carbon black in the aspect 1 is relative to 100 parts by weight. The rubber component 5 is about 20 to 100 parts by weight, preferably 40 to 90 parts by weight, more preferably 40 to 80 parts by weight. Further, the blending amount of the modified calcium carbonate is compared with 100 weights. The rubber knee component is about 5 to 18 parts by weight, preferably 1 to 18 parts by weight, and more preferably 3 to 15 parts by weight. The aspect 1 can maintain the processability and mechanical properties of the rubber knee composition. In the case of H), it is particularly effective to improve the flex crack resistance and the Mooney vulcanization time. In 100 parts by weight of the shuttle ^ right component 丨: 2 〇 ~ 8 〇 之 二 ^ ^ 成份 成份 成份 成份 成份 成份 成份 成份 成份 5 5 5 5 5 5 5 5 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四 四The Jingsha Fine Sword is a rubber composition with a weight of 15%.

Specific examples of the rubber composition in the present invention include, for example, aspect 2: with respect to 100 parts by weight of a rubber selected from at least one of natural rubber and synthetic rubber, a specific amount is blended with a dioxin-cut, The component 2 has (1) a dioxygen layer, and (9) is selected from the group consisting of a fatty acid, a lipid salt, a fatty acid vinegar, a 20 resin acid, a resin acid salt, and a resin acid vinegar. And (4) a modified carbonic acid layer of the Wei coupling agent layer, and a composition of the component 3 > 6 Xiyuan coupling agent. The blending amount of cerium oxide is preferably about 20 parts by weight with respect to the rubber component of the parts by weight, and preferably 40 parts by weight. Further, the blending amount of the modified calcium carbonate having (1) 25 1352718. The cerium oxide layer, the (11) organic acid layer, and the (iii) decane coupling agent layer is 〇5~ with respect to 1 part by weight of the rubber component. It is preferably about 15 parts by weight, more preferably 1 to 15 parts by weight, and more preferably 3 to 15 parts by weight. - the blending amount of the decane coupling agent is about 5% by weight of 〇.1 to 30, and about 1 to 20% by weight, and preferably about 3 to 1% by weight. For better. The rubber composition of the aspect 2, for example, after blending the ceria and the decane coupling agent in at least one rubber selected from the group consisting of natural rubber and synthetic rubber, ^ is blended with (1) cerium oxide layer, (1) organic acid The layer and (iii) three layers of modified calcium carbonate of the decane coupling agent layer 10 are then produced by mixing. The order of mixing of the cerium oxide, the Shixiayuan coupling agent and the modified carbonic acid can be appropriately set as needed. Further, the composition of the aspect 2 can be produced by using partially modified calcium carbonate having two layers of (1) a hafnium oxide layer and (ii) an organic acid layer. For example, after blending the ceria and the decane coupling agent in the rubber 15 rubber selected from at least one of natural rubber and synthetic rubber, blending the layer having the (1) cerium oxide layer and (ii) the organic acid layer The calcium carbonate is modified and then produced by mixing. Further, after blending cerium oxide and modified calcium carbonate having two layers of (1) cerium oxide layer and (ii) organic acid layer in a rubber selected from at least one of natural rubber and synthetic rubber, blending decane The coupling agent is then made by mixing. By adding a partially modified carbon strontium calcium and a decane coupling agent having (i) an oxidized layer and (ii) an organic acid layer to the rubber composition and mixing, the decane couple & agent is attached and has (1) The ruthenium dioxide layer and (ii) the organic acid layer partially modify the surface of the calcium carbonate, and form (1) ruthenium dioxide 26 layer, (11) organic acid layer and (iii) decane coupling agent in the rubber composition. Three layers of modified calcium carbonate. Zinc 9 This produces a rubber composition comprising modified calcium carbonate having a (1) cerium oxide layer, (ii) an organic acid layer and an environmental coupling layer. The quality mountain has a part of the (1) dioxide dioxide layer and (ii) the organic acid layer, and the partial modification of the carbon and the decane coupling agent are respectively added to the rubber' and formed in the rubber composition: a ~ repeated modification When the amount of carbonic acid is about 5% by weight, the amount of the addition of the sulphur coupling agent to the rubber composition is preferably about 0.1 to 35% by weight, and preferably about 0.1 to 33% by weight. The aspect 2 does not impair the workability and mechanical properties of the rubber composition, and can improve the physical properties of the unvulcanized rubber such as the Mooney vulcanization time, and can particularly achieve an excellent effect of improving the tensile strength and the permanent elongation. Rubber The rubber article of the present invention is formed into a rubber composition of the present invention by a known method, and if necessary, obtained by vulcanization. Examples of rubber articles include tire treads, soles, rubber bands, rubber sheets (rubber sheets), rubber rollers, rubber hoses, 〇-rings, oil seals, etc., engine gaskets, rubber bushings, rubber couplings. Anti-vibration rubber products, rubber seals such as face frames, foam rubber, etc. Among them, 'is particularly suitable for use as a tire tread. Examples of the molding method include extrusion molding, injection molding, calender processing, and extrusion molding. Further, the vulcanization method may be exemplified by mold forming vulcanization (squeezing), plate vulcanization, direct vapour vulcanization, high-frequency heating continuous vulcanization, and the like. Further, the rubber composition containing the foaming agent and the foaming aid can be formed or pulverized to obtain a foamed rubber (sponge). The condition of the squat can be set locally according to the desired piece or (4). Also, the vulcanized strip is right. "疋 仵 仵 且 且 且 且 且 且 且 且 且 且 且 且 且 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左 左For example, the industry 杳 η 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 域 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Face rubber composition. 15 "In the rubber composition of the present invention, in particular, it contains and uses carbon black and modified rubber, and does not impair the storage stability of the unfiled rubber" and has excellent flex crack resistance (four) which improves the physical properties of the vulcanized rubber. Further, the rubber composition of the present invention contains, in particular, a combination of a silica dioxide coupling agent and a modified carbon ruthenium compound, and does not impair the mechanical strength of the rubber composition which only pushes the dioxotomy. Moreover, it has an excellent effect of remarkably improving the storage stability of the rubber. 20 Further, the rubber product of the present invention is excellent in workability because it is a rubber composition which is blended in a specific ratio with the above specific components. It has excellent performance in terms of flex cracking and the like. t. Performing a cold type. Hereinafter, the present invention will be described in detail by way of examples and test examples, but the present invention will not be Any limitation 28 1352718 • Preparation Examples 1 to 2 and Comparative Examples 1 to 4 Materials The following materials were used in Examples 1 to 2 and Comparative Examples 1 to 4. 5. Oil Show 8611: Claw 8 17781 (Combined with Styrene 23.5%, as opposed to 100 parts by weight of styrene butadiene dip in 37.5 phr of stretching oil, JSR (share) system; • carbon black: Asahi #80, ISAF, Asahi carbon (Xu Liyi Qiu: /) (share) system; Cerium oxide: white carbon, Nipsil AQ, Japanese cerium oxide industry (Day 10 シ y force) (share) system; • decane coupling agent: bis (3_[triethoxy decyl] propyl) _ four Sulfide, Si69, made by Degussa; • Zinc oxide: Zinc oxide, just like chemical; • Stearic acid: LUNAC S — 50, Kao system; 15 • Naphthenic oil: NP — 24, Idemitsu Kosan ;; anti-aging agent: NOCRAC 224, Ou Nei emerging chemical industry (shares) system; • vulcanization accelerator 1 : NOCCELER — D, Da Nei emerging chemical industry (shares); 20 • vulcanization accelerator 2 : NOCCELER - CZ, Dae Neng Xin Chemical Industry Co., Ltd.; • Sulfur, powder sulfur, fine well chemical system; • Modified calcium carbonate: The modified calcium carbonate used in the examples and comparative examples is prepared as follows. The synthetic calcium carbonate slurry having a BET specific surface area of 75 m 2 /g is heated by a sufficient stirring surface. The slurry is added at room temperature to a sodium silicate (stone). After the acid solution (made by Wako Pure Chemical Industries, 193-08185), the aqueous solution is used as the amount of cerium oxide, and a 3.5% diluted aqueous hydrochloric acid solution is added dropwise while stirring, and the activated carbon dioxide hydrazine is formed to treat the carbonic acid in the cracking liquid. Calcium surface. The amount of sodium citrate aqueous solution and dilute hydrochloric acid aqueous solution is adjusted to 7 weights relative to the synthesis of 1 part by weight of calcium carbonate relative to the amount of synthetic calcium carbonate obtained by cerium oxide hydrosol. Next, add sodium hydroxide and stir to 9 〇 ° C, and add 5 parts by weight of saponified mixed fatty acid (containing oleic acid, stearic acid, palmitic acid and other fatty acid mixtures (Wako Pure Chemical, Oleic acid (159 - 〇〇 246), stearic acid (199 - 10995), palmitic acid (165 - 00102))), followed by dehydration, drying and pulverization to form calcium carbonate having a layer of cerium oxide and a layer of fatty acid Powder (calcium carbonate A) 0 15 The obtained calcium carbonate A was stirred with a stirrer while 2.0 parts by weight of the above calcium carbonate A in a part by weight of bis-(3-[triethoxydecylalkyl]-propene. Base) tetrasulfide (Degussa) Further, the Si69) spray was heated and dried at 100 ° C for 60 minutes after mixing for a minute to obtain a modified calcium carbonate having three layers of a layer of a cerium oxide layer, an organic acid layer and a layer of a decane coupling agent. 20 <Win composition and rubber product _ The materials shown in Table 1 or Table 2 were mixed at the ratios specified in Table 1 or Table 2, and the rubbers of Examples 1 to 2 and Comparative Examples 1 to 4 were produced. Composition. A kneading machine having a volume of 31^ and two 8-inch drums were used as the mixing device. The mixing conditions were a casting volume of 70% (2.1 L), a rotation speed of the drum of 30 rpm, a piston pressure of 30 1352718 ^ O. IMPa, a mixing start temperature of 30 ° C, and a mixing time of 7 minutes. Further, each of the obtained rubber compositions was subjected to an optimum vulcanization time tc (90) calculated by a sulphurization tester (manufactured by JSR, test temperature: 160 ° C) to 160. (: A rubber sheet having a thickness of 2 mm or a test piece used in the evaluation method described later was prepared by press-vulcanization molding. Evaluation The rubber compositions of Examples 1 to 2 and Comparative Examples 1 to 4 were evaluated.

The Mooney curing time was investigated by the physical properties of the vulcanized rubber. Further, in order to evaluate the physical properties of the rubber after vulcanization, relevant tensile tests, tensile tests, hardness, and permanent were performed on various molded bodies (rubber sheets or test pieces) obtained by vulcanization molding in Examples 丨 to 2 and Comparative Examples 1 to 4. Test for elongation and flex crack resistance. L Mooney curing time 15

20 According to the method specified in JIS K 6300, the measurement was made using the threshold viscosity of Shimadzu Corporation. At the test temperature of 1251: after preheating for 1 minute, the time from the minimum torque to the rise of 5 points is started. 2. Tensile test (elasticity, tensile strength) The machine was subjected to the following test items using the Shawl tensile test using the method specified in Z:ISK 6251. Tensile modulus: Tensile strength at 3〇〇% elongation; ^ Sex strength. The load at the time of cutting divided by the value of the test piece area; showing relative; ^ Table is not relative to the tensile strength of the elongation, and the tensile strength table The strength of the weight. ί·hardness

31 1352718 Measured according to the method specified in JIS K 6253 using a Type Α hardness tester made by a polymer tester. 4. Pulling strength The method specified in 6252' uses the Shawler tensile tester at: The mouth carries the remaining amount. A test piece using a crescent type (with a missing mouth). The more this value, the more difficult it is to damage the cracks or fragments caused by sporadic defects. 5 · Permanent elongation Use the No. 1 shape of the bell shape and the marking line is 40mm. Extend the tension of 2 above. The amount of elongation at the time of cutting in the test was maintained for four (4) minutes. After 3 minutes, the external force was removed and then allowed to stand for 3Q minutes, and the residual elongation at this time was measured. This value means that the more difficult it is to cause the skew caused by the stress, in particular, the composition can predict the improvement (decrease) in the rotational resistance for the tire tread rubber. 15 6· For the method of the flexural cracking property, the Demardia (mouth 10) flexural testing machine manufactured by Ueshima Seisakusho Co., Ltd. was used to measure the number of deflections (cycles) of the turtle to 10 mm during the bending. The thickness of the test piece used was 6 rmmm 20 and the reciprocating motion was repeated every minute. The test piece clamp has a moving distance of 57 legs, and the largest set of clips (4) is 75_. When it is used as a tire tread, it is better to use the number of deflections. 2 The number of the tune is less, and the appearance of the tire surface is damaged and it becomes a fragmentation. The result of the above evaluation is shown in Table 2 and Table 2. 32 [Table i] Test material name Example 1 Comparative Example 1 Comparative Example 2 Oil show SBR (pure rubber) [parts by weight] 100 100 100 Carbon black [parts by weight] 50 50 50 Modified carbon strontium calcium [parts by weight] 10 — 30 Zinc Oxide [Parts by Weight] 3 3 3 Stearic Acid [Parts by Weight] 2 2 2 Aging Preventing Agent [Parts by Weight] 1 1 1 Naphthenic Oil (including rubber oil) [Parts by weight] 40.5 40.5 40.5 Vulcanization accelerator 1 [parts by weight] 1 1 1 vulcanization accelerator 2 [parts by weight] 1 1 1 sulfur yellow [parts by weight] 2 2 2 [unvulcanized rubber properties] Mooney vulcanization time t5, 125 ° C 35.2 31.5 32.0 [Vulcanized rubber properties] 300 % Elasticity [MPa] 5.4 5.5 5.2 Tensile strength [MPa] 17.2 15.8 19.2 Hardness 50 50 49 Tensile strength [N/mm] 26.1 24.6 29.8 Permanent elongation [%] 4.8 4.5 4.6 Deflection cracking [kc /2 - 10 mm] 8.0 4.2 8.7 1352718 From the results of Table 1, it is understood that the rubber composition of Example 1 has a longer Mooney vulcanization time than the rubber compositions of Comparative Examples 1 and 2. In Comparative Example 1, the Mooney vulcanization time was short, the tensile strength and the flex crack resistance were small, while in Comparative Example 2, the tensile strength and the flex crack resistance were good, but the Mooney vulcanization time was improved. Small and elastic rate is also easy to reduce. On the other hand, in the first embodiment, the Mooney vulcanization time was long, and various rubber physical properties such as elastic modulus, tensile strength, and flex crack resistance were obtained. -it:, ». -^Λ -· 33 1352718 Reference [Table 2] Test material name Example 2 Comparative Example 3 Comparative Example 4 Oil show SBR (pure rubber) [parts by weight] 100 100 100 Carbon black [parts by weight] 50 50 50 modified calcium carbonate "[ parts by weight] 5 - 20 decane coupling agent [parts by weight] 5 5 5 zinc oxide [parts by weight] 3 3 3 stearic acid [parts by weight] 2 2 2 aging preventive agent [parts by weight ] 1 1 1 naphthenic oil (including rubber oil) [parts by weight] 40.5 40.5 40.5 vulcanization accelerator 1 [parts by weight] 1 1 1 vulcanization accelerator 2 [parts by weight] 1 1 1 sulfur yellow [parts by weight] 2 2 2 [Unvulcanized rubber properties] "7 Ϊ 硫化 vulcanization time t5, 125 〇 C 44.3 39.8 36.2 [Vulcanized rubber physical properties] 300% elastic modulus [MPa] 4.3 3.9 4.6 Tensile strength [MPa] 17.8 19.6 17.0 Hardness 56 54 60 + tensile strength [N/mm] 33.8 31.5 45.1 """" Fruit elongation [%] 7.6 8.8 7.4 Flexibility crack resistance [kc/2-^ 10mm] 5.2 4.4 4.9 It is clear from the results of Table 2. The rubber composition of Example 2 had a longer Mooney vulcanization time than the rubber compositions of Comparative Examples 3 to 4. The rubber composition door of Comparative Example 3 In the rubber composition of Comparative Example 4, the Mooney vulcanization time was short and the tensile strength was easily lowered. On the other hand, the rubber composition of the present invention of Example 2 'Monni vulcanization 34 1352718 It has a long time and can be obtained from various physical properties such as elastic modulus and flex crack resistance. Simple description of L pattern 3 No 5 [Explanation of main component symbols]

./·Production, ν V. ·.' 35

Claims (1)

1352718 Patent application No. 94102494 Patent application for the replacement of this patent, the scope of the patent application: 1. One-one-one-one 1. A rubber-knitted product containing 100 parts by weight selected from natural rubber and synthetic At least one rubber of rubber, and component 1 and component 2', wherein the component 1 is 20 to 1 part by weight selected from the group consisting of (1) 5 carbon black, (2) cerium oxide, and (3) carbon. Any of ~(3) in the group consisting of a mixture of black and cerium oxide, and the above-mentioned component 2 is 0.5 parts by weight or more to less than 20 parts by weight of the modified layer having the #2 cerium oxide layer and the decane coupling agent layer Calcium carbonate 2. A rubber composition comprising 100 parts by weight of a rubber selected from at least one of natural rubber and 10 synthetic rubber, and component 1 and component 2, and 'the aforementioned component 1 is 20 to 100 parts by weight Any one of (1) to (3) selected from the group consisting of (1) carbon black, (2) cerium oxide, and (3) a mixture of carbon black and cerium oxide, and the aforementioned component 2 is 0.5. Parts by weight or more to less than 20 parts by weight (〇15 cerium oxide layer, (ii) selected from the group consisting of fat And an organic acid layer obtained by treating at least one of a group consisting of a fatty acid salt, a fatty acid hydrazine, a resin acid, a resin acid salt, and a resin acid ester, and (iii) a modified calcium carbonate having a decane coupling agent layer. 3. The rubber composition of claim 1 or 2 wherein the aforementioned component 2〇1 is a mixture of (3) carbon black and cerium oxide, and in a weight ratio, a mixture of double black and bismuth fossils The ratio is 0.5: 99·5 to 99.5: 0.5. 4. The rubber composition according to claim 1 or 2, wherein the component 1 is (2) cerium oxide, and the rubber composition further comprises component 3, And the blending amount of the above-mentioned component 3 relative to cerium oxide is 0.1 to 3 〇 weight 36 1352718 Patent application No. 94! 〇 2494 Patent application patent garden replacement replacement revision period: August 31, 2011 The rubber composition of the first or second aspect of the invention, wherein the component 1 is (3) a mixture of carbon black and cerium oxide and the rubber composition further comprises a component 3' and The amount of the above component 3 is 5 to 3 with respect to the amount of cerium oxide blended. 0% by weight of a decane coupling agent. 6. The rubber composition of claim 3, wherein the aforementioned component 1 is a mixture of (3) carbon black and cerium oxide, and the rubber composition φ material further comprises component 3, And the component 3 is a decane coupling agent having a holding amount of 0.1 to 30% by weight based on the amount of the hair of the oxidized hair. 10 7· a rubber product, which is composed of the rubber of any one of the claims 1 to 6. The object is formed. t 37