WO2006059503A1 - 空気入りタイヤ - Google Patents
空気入りタイヤ Download PDFInfo
- Publication number
- WO2006059503A1 WO2006059503A1 PCT/JP2005/021251 JP2005021251W WO2006059503A1 WO 2006059503 A1 WO2006059503 A1 WO 2006059503A1 JP 2005021251 W JP2005021251 W JP 2005021251W WO 2006059503 A1 WO2006059503 A1 WO 2006059503A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rubber
- group
- natural rubber
- pneumatic tire
- meth
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F253/00—Macromolecular compounds obtained by polymerising monomers on to natural rubbers or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Definitions
- the present invention relates to a pneumatic tire.
- Rubber constituting the steel belt portion of a pneumatic tire is an important rubber involved in the durability of the tire.
- the methods (a) to () also have a problem that the viscosity of the rubber composition is increased and the processability is lowered.
- natural rubber has been mainly used as a case member as a material having excellent fracture resistance.
- synthetic rubbers such as styrene-butadiene copolymer rubber and polybutadiene rubber that can reduce the loss by terminal modification technology
- natural rubber has not been able to reduce the loss by improving the rubber component until now. Because of this, the case rubber was able to greatly reduce rolling resistance.
- the present invention solves the above-mentioned conventional problems, and is a belt portion made of a rubber composition that has excellent reinforcing properties, high hardness, low heat generation, excellent deterioration resistance, and excellent adhesion to steel cords.
- the first object is to provide a pneumatic tire that is remarkably excellent in durability.
- the pneumatic tire of the first aspect of the present invention is a modified natural rubber obtained by graft-polymerizing a polar group-containing monomer to a natural rubber latex, coagulating and drying the rubber composition constituting the belt portion. It is characterized by including.
- this effect improves low-loss characteristics, reduces heat generation that contributes to deterioration during traveling, and suppresses the progress of deterioration.
- the use of natural rubber is presumed to be due to an action mechanism in which fillers such as carbon black and rubber interact positively, reinforcing properties are improved, and crack propagation resistance is improved.
- the part to which the rubber composition containing the modified natural rubber is applied is preferably one or more rubbers selected from the group consisting of a belt coating rubber, a belt end rubber and an inter-belt rubber in the belt portion.
- the second aspect of the present invention is to provide a pneumatic tire excellent in low rolling resistance without impairing durability by improving the rubber properties of ply coating rubber, squeegee rubber, and tie rubber. The purpose.
- the pneumatic tire of the second aspect of the present invention comprises a rubber composition containing a modified natural rubber obtained by graft polymerization of a polar group-containing monomer to a ply-coating rubber strength natural rubber latex, coagulated and dried. It is characterized by that.
- the pneumatic tire of the third aspect of the present invention comprises a rubber composition containing a modified natural rubber obtained by graft polymerization of a polar group-containing monomer on a squeegee rubber natural rubber latex, coagulated and dried. It is characterized by.
- the pneumatic tire according to the fourth aspect of the present invention is composed of a rubber composition containing a modified natural rubber in which a tie rubber is obtained by graft polymerization of a polar group-containing monomer to natural rubber latex, coagulation, and drying. It is characterized by.
- This modified natural rubber is obtained by graft polymerizing a polar group-containing monomer to natural rubber latex, solidifying, and drying.
- the natural rubber latex is normal, and includes field latex, ammonia-treated latex, centrifugal concentrated latex, deproteinized latex treated with a surfactant or an enzyme, and combinations thereof. Can do.
- the polar group-containing monomer is not particularly limited as long as it is a monomer having at least one polar group in the molecule! ⁇ .
- Specific examples of polar groups of the polar group-containing monomer include amino groups, imino groups, nitrile groups, ammonium groups, imide groups, amide groups, hydrazo groups, azo groups, diazo groups, hydroxyl groups.
- Examples thereof include silyl groups and tin-containing groups.
- One of these polar group-containing monomers may be used alone, or two or more thereof may be used in combination.
- the polar group-containing monomer may contain only one kind of these polar groups, or may contain two or more kinds.
- the amino group-containing monomer includes a polymerizable monomer having at least one amino group selected from primary, secondary, and tertiary amino groups in one molecule.
- a tertiary amino group-containing monomer such as dialkylaminoalkyl (meth) acrylate is particularly preferred.
- (meth) acryl means “acryl or methacryl”
- (meth) acrylate” means “acrylate or metatalylate”.
- Examples of the primary amino group-containing monomer include acrylamide, methacrylamide, 4-vinyl phosphorus, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, amino pill ( (Meth) acrylate, aminobutyl (meth) acrylate and the like.
- Examples of the secondary amino group-containing monomer include:
- Examples of the tertiary amino group-containing monomer include ⁇ , ⁇ disubstituted aminoalkyl acrylate, ⁇ , ⁇ disubstituted aminoalkyl acrylamide, and vinyl compounds having a pyridyl group.
- Examples of ⁇ , ⁇ disubstituted aminoalkyl acrylates include ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylaminomethyl (meth) acrylate, ⁇ , ⁇ ⁇ ⁇ ⁇ dimethylaminoethyl (meth) acrylate, ⁇ , ⁇ -dimethylaminopropyl.
- N, N dimethylaminoethyl (meth) acrylate, N, N jetylaminoethyl (meth) acrylate, N, N dipropylaminoethyl (meth) acrylate, N, N diamino aminoethyl (meth) acrylate Rate, N-methyl N-ethylaminoethyl (meth) acrylate, etc. are preferred!
- N, N disubstituted aminoalkylacrylamides include N, N dimethylaminomethyl (meth) acrylamide, N, N dimethylaminoethyl (meth) acrylamide, and N, N-dimethylaminopropyl (meth) acrylamide.
- N, N dimethylaminopropyl (meth) acrylamide, N, N jetylaminopropyl (meth) acrylamide, N, N dioctylaminopropyl (meth) acrylamide and the like are particularly preferable.
- Examples of the bur compound having a pyridyl group include 2 vinyl pyridine, 3 vinyl pyridine, 4 butyl pyridine, 5-methyl 2 butyl pyridine, 5 ethyl 2 bis pyrrolidine and the like. Of these, 2-bulupyridine, 4-bulupyridine and the like are particularly preferable.
- nitrogen-containing heterocyclic ring of the monomer having a nitrogen-containing heterocyclic group for example, pyrrole, histidine, imidazole, triazolidine, triazole, triazine, pyridine, pyrimidine, virazine, indole, quinoline, purine, phenazine, Examples include pteridine and melamine.
- Nitrogen-containing heterocycles may contain other heteroatoms in the ring! /.
- nitrile group-containing monomer examples include (meth) acrylonitrile, cyanobiuridene and the like.
- Examples of the hydroxyl group-containing monomer include polymerizable monomers having at least one primary, secondary, and tertiary hydroxyl group in one molecule.
- Examples of such a monomer include a hydroxyl group-containing unsaturated carboxylic acid monomer, a hydroxyl group-containing benzene monomer, and a hydroxyl group-containing benzene ketone monomer.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2- Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; polyalkylenes such as polyethylene glycol, polypropylene glycol, etc.
- Mono (meth) acrylates of glycols (alkylene glycol units, eg 2 to 23); N-hydroxymethyl (meth) acrylamide, N— (2-hydroxyethyl) (meth) acrylamide, N, N —Hydroxy such as bis (2-hydroxymethyl) (meth) acrylamide O-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, o-hydroxy ex-methino styrene, m-hydroxy ex-methino styrene, p-hydroxy-ex-methyl styrene, p- There are hydroxyl group-containing bur aromatic compounds such as burbendyl alcohol; and (meth) atarylates.
- hydroxyl group-containing unsaturated carboxylic acid monomers hydroxyalkyl (meth) acrylates, and hydroxyl group-containing vinyl aromatic compounds are preferred, particularly hydroxyl group-containing unsaturated carboxylic acid monomers.
- hydroxyl group-containing unsaturated carboxylic acid monomer include derivatives such as esters, amides, anhydrides, etc. such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, etc., particularly acrylic acid, methacrylic acid, etc.
- the ester compound is preferable.
- carboxyl group-containing monomer examples include unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, tetraconic acid, cinnamic acid; or phthalic acid, succinic acid, adipic acid Such as a monoester of a non-polymerizable polyvalent carboxylic acid such as (meth) aryl alcohol and a hydroxyl group-containing unsaturated compound such as 2-hydroxyethyl (meth) acrylate. Examples thereof include carboxyl group-containing esters and salts thereof. Of these, unsaturated carboxylic acids are particularly preferred!
- Examples of the epoxy group-containing monomer include (meth) aryl glycidyl ether, glycidyl (meth) acrylate, 3, 4-oxycyclohexyl (meth) acrylate.
- alkoxysilyl group-containing monomer examples include (meth) atarioxymethyltrimethoxysilane, (meth) atalyoxymethylmethyldimethoxysilane, (meth) atarioxymethyldimethylmethoxysilane, and (meth) atari.
- Examples of the tin-containing monomer include, for example, allyltri- ⁇ -butyltin, allyltrimethyltin, allyltriphenyltin, allyltri- ⁇ -octyltin, (meth) acryloxy- ⁇ -butyltin, and (meth) acrylic.
- the modified natural rubber for example, by adding a polar group-containing monomer to natural rubber latex, After adding an initiator for graft polymerization, emulsion polymerization is performed, and then the resulting polymer is solidified and dried.
- the initiator for graft polymerization is not particularly limited, and various initiators such as an initiator for emulsion polymerization can be used, and the addition method thereof is not particularly limited.
- examples of commonly used initiators include benzoyl peroxide, hydrogen peroxide, tamen hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, 2,2-azobisisobutyoxy-tolyl, 2 , 2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2-diaminopropane) dihydrochloride, 2,2-azobis (2,4-dimethylvalero-tolyl), potassium persulfate, sodium persulfate, persulfate Examples include ammonium sulfate.
- a redox polymerization initiator In order to reduce the polymerization temperature, it is preferable to use a redox polymerization initiator.
- the reducing agent used in combination with the peracid compound used as a powerful redox polymerization initiator include tetraethylenepentamine, mercaptans, sodium acid sulfite, reducing metal ions, ascorbic acid and the like.
- a combination of tert-butyl hydroberoxide and tetraethylenepentamine is preferred as a redox polymerization initiator.
- Graft polymerization may be general emulsion polymerization in which the above-mentioned polar group-containing monomer is added to natural rubber latex and polymerized while stirring at a predetermined temperature.
- water and an emulsifier previously added to the polar group-containing monomer and sufficiently emulsified may be added to the natural rubber latex, or the polar group-containing monomer may be directly added to the natural rubber latex. If necessary, an emulsifier may be added before or after the monomer is added.
- the emulsifier is not particularly limited, and examples thereof include a noion surfactant such as polyoxyethylene lauryl ether.
- the modified natural rubber is prepared by charging the above-described components into a reaction vessel, and at 30 to 80 ° C for 10 minutes to 7 hours.
- a modified natural rubber latex is obtained by carrying out an interreaction to carry out graft polymerization, and this modified natural rubber latex is coagulated, washed, and then dried using a dryer such as a vacuum dryer, an air dryer or a drum dryer. Can be obtained.
- the graft amount of the polar group-containing monomer is preferably from 0.01 to 5.0% by weight, more preferably from 0.1 to 3.0% by weight, based on the rubber content of the natural rubber latex. 2 to 1.0% by weight is particularly preferred.
- the graft amount of the polar group-containing monomer is less than 0.01% by weight, the effect of the present invention by using this modified natural rubber cannot be sufficiently obtained. Natural rubber inherent properties such as elasticity and S—S characteristics (stress-strain curve in a tensile testing machine) may be impaired and processability may be reduced.
- Rubber compositions such modified natural rubber as a rubber component, preferably 10 weight 0/0 or more, more preferably 40 wt% or more, particularly 60 wt% or more, more preferably 60 to: LOO Weight %, especially 80 to: LOO those containing by weight 0/0.
- the content of the modified natural rubber is less than the lower limit, the effect of the present invention by using the modified natural rubber cannot be sufficiently obtained.
- Examples of other rubber components used in combination with the modified natural rubber include ordinary natural rubber and Gen-based synthetic rubber.
- Examples of the gen-based synthetic rubber include styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), and ethylene-propylene copolymer. These other rubber components may be used alone or in combination of two or more.
- the rubber composition as a rubber component, and the modified natural rubber 30-60 wt 0/0, SBR, Yogu also by containing 10 to 30% by weight of diene-based synthetic rubber BR like, good low Both heat generation and high fracture resistance can be achieved.
- the rubber composition preferably contains carbon black as a filler.
- the compounding amount of carbon black is preferably 30 to 120 parts by weight with respect to 100 parts by weight of the rubber component in the rubber composition. If the blending amount is less than 30 parts by weight, the reinforcing effect and other physical property improving effects due to the blending of carbon black cannot be obtained sufficiently, and if it exceeds 120 parts by weight, the workability and the like are lowered.
- any commercially available carbon black can be used, among them SAF, ISAF, It is preferable to use HAF, FEF, GPF grade carbon black.
- any commercially available silica can be used, and wet silica, dry silica, and colloidal silica are preferably used.
- the BET specific surface area of silica is preferably 150 m 2 / g or more, more preferably 170 m 2 / g or more, particularly preferably 190 m 2 Zg or more.
- commercial products such as “Nipsil AQ” and “Nipsil KQ” manufactured by Tosoh Silica Co., Ltd. can be used.
- carbon black and silica either one may be used alone, or two or more may be used in combination.
- the modified natural rubber when silica is compounded in the rubber composition, as the modified natural rubber, it is possible to use a modified natural rubber obtained by graft polymerization of an alkoxysilyl group-containing monomer as a modified natural rubber.
- U which is preferable in that the modified natural rubber is strongly bonded and an excellent compounding effect can be obtained by the interaction between silica and the modified natural rubber.
- the rubber composition is usually used in the rubber industry as required !, such as other reinforcing fillers, vulcanizing agents, vulcanization accelerators, anti-aging agents, softening agents. Etc. can be appropriately blended according to the purpose.
- the modified natural rubber is used in one or more selected from the group part consisting of a belt portion, preferably a belt coating rubber, a belt end rubber, and an inter-belt rubber. It is comprised by the rubber composition containing.
- the pneumatic tire of the first aspect can have the same configuration as that of a conventional pneumatic tire except that the belt portion is made of the rubber composition containing the modified natural rubber. There is no limit and it is manufactured according to a conventional method.
- the pneumatic tire according to the second to fourth aspects of the present invention is made of a rubber composition containing the above modified natural rubber, such as ply coating rubber, squeegee rubber, and tie rubber.
- Pneumatic tires can be ply-coated rubber, squeegee rubber or Only one of the rubbers may be composed of the rubber composition, or two or all of these may be composed of the rubber composition.
- This pneumatic tire can have the same structure as a conventional pneumatic tire except that ply-coating rubber, squeegee rubber or tie rubber is composed of a rubber composition containing the above modified natural rubber. There is no particular limitation on the above, and it is produced according to a conventional method.
- the pneumatic tire of the present invention is effective for various pneumatic tires such as pneumatic tires for heavy loads such as buses, trucks and airplanes, and pneumatic tires for race cars such as passenger cars and motor sports (MS). Applied.
- the first aspect of the present invention will be described more specifically with reference to production examples, examples and comparative examples.
- the first aspect is limited to the following examples as long as it does not exceed the gist thereof. It is not a thing.
- Production Example 1 Method for producing modified natural rubber
- the field latex was centrifuged at a rotation speed of 7 500 rpm using a latex separator (manufactured by Saito Centrifugal Co., Ltd.) to obtain a concentrated latex having a dry rubber concentration of 60%.
- This concentrated latus tas lOOOOg is put into a stainless steel reaction vessel equipped with a stirrer and a temperature control jacket, and 10 ml of water and 90 mg of emulsifier (Emargen 1108, manufactured by Kao Corporation) are added to 4 burpyridine 3. Og in advance.
- the emulsified mixture was added with 990 ml of water, and the mixture was stirred for 30 minutes with a force S without nitrogen replacement.
- 1.2 g of tert-butyl hydroperoxide and 1.2 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C. for 30 minutes to obtain a modified natural rubber latex.
- the modified natural rubber latex was then coagulated by adding formic acid and adjusting the pH to 4.7.
- the solid thus obtained was treated five times with a creper, crushed through a shredder, and dried at 110 ° C. for 210 minutes with a hot air dryer to obtain modified natural rubber A.
- the weight ratio of the modified natural rubber A thus obtained was confirmed to be 100%.
- the modified natural rubber is When the homopolymer was separated by extraction with oil ether and then extraction with a 2: 1 mixture of acetone and methanol, the analytical power of the extract was not detected, and the homopolymer was not detected. It was confirmed that 100% was introduced into the natural rubber molecule.
- the rubber composition having the composition shown in Table 1 was evaluated as follows, and the results are shown in Table 1.
- Modified natural rubber 4 vinyl pyridine produced in Production Example 1 0.5% modified natural rubber Silica: “Nipsil AQ” manufactured by Tosoh Silica Corporation
- Carbon black N326 "Asahi # 70L” manufactured by Asahi Carbon Co., Ltd.
- Cobalt salt “DICNATE NBC-II” manufactured by Dainippon Ink & Chemicals, Inc.
- Vulcanization accelerator “Noxera DZ” (N, N dichlorohexyl-2-benzothiazolylsulfenamide) manufactured by Ouchi Shinsei Engineering Co., Ltd.
- Anti-aging agent “NOCRACK NS-6” manufactured by Ouchi Shinsei Chemical Co., Ltd.
- a rubber composition vulcanized under vulcanization conditions (160 ° CX for 14 minutes) has an elongation at break before and after a deterioration test of 100 ° CX for 24 hours in air.
- JIS K6301-1995 (No. 3 test) It measured according to the piece) and calculated by the following formula.
- Retention rate 100 X (Elongation at break after deterioration) / (Elongation at break before deterioration)
- a rubber composition vulcanized under vulcanization conditions (160 ° C x 14 minutes) can be ignored for 3 days after standing at 25 ° C for 3 days, and the whiteness caused by sulfur bloom can be ignored. The ones with “”, white, and the part with “X” were judged as “X”.
- a steel cord with a brass finish (IX 5 structure, strand diameter: 0.225 mm) is arranged in parallel at 12.5 mm intervals, and the steel cord is coated with a rubber composition from both sides to create a sample.
- Vulcanized under vulcanization conditions 160 ° CX 10 minutes
- the steel cord pulled out in accordance with AST MD-2229 bow I cut out cord surface, covered with rubber, The surface area ratio was determined visually.
- a rubber composition vulcanized under vulcanization conditions (160 ° C x 14 minutes) is punched into a dumbbell shape, and a sample with a 5mm pre-crack in the center is 80 ° C with a chuck distance of 20 ° using a fatigue tester.
- a stroke of 7 Hz with a constant stress of mm was given, and the number of times until complete rupture was shown as an index, with the case of Comparative Example 1 being 100.
- Vulcanization accelerator 1.0 1.0 1.0 1.0 1.0 1.0 2.0 1.0 parts
- the rubber composition containing the modified natural rubber according to the present invention has low loss characteristics, low heat generation, deterioration resistance, adhesion to a steel cord, and crack growth resistance. According to the pneumatic tire of the present invention in which such a rubber composition is used for the belt portion, it is apparent that a pneumatic tire excellent in durability is provided.
- the second to fourth aspects of the present invention will be described more specifically with reference to production examples, examples and comparative examples.
- the second to fourth aspects are as follows unless they exceed the gist of the present invention. It is not limited to the examples.
- Production Example 2 Production Method of Modified Natural Rubber A
- the field latex was centrifuged at a rotation speed of 7 500 rpm using a latex separator (manufactured by Saito Centrifugal Co., Ltd.) to obtain a concentrated latex having a dry rubber concentration of 60%.
- a latex separator manufactured by Saito Centrifugal Co., Ltd.
- To obtain a concentrated latex having a dry rubber concentration of 60% Put this concentrated latus tasOOg into a stainless steel reaction vessel equipped with a stirrer and temperature control jacket, and add 10 ml of water and 90 mg of emulsifier (Emargen 1108, manufactured by Kao Corporation) to 2-Burpyridine 3. Og. Add the emulsified powder together with 990 ml of water, and replace it with nitrogen. The mixture was stirred for 30 minutes. Next, 1.2 g of tert-butyl hydroperoxide and 1.2 g of tetraethylenepentamine were added as polymerization initiators and reacted at 40 ° C
- the modified natural rubber latex was then coagulated by adding formic acid and adjusting the pH to 4.7.
- the solid thus obtained was treated five times with a creper, crushed through a shredder, and dried at 110 ° C. for 210 minutes with a hot air dryer to obtain modified natural rubber A.
- the weight ratio of the modified natural rubber A thus obtained was confirmed to be 100%.
- the conversion rate of 2-vinylpyridine as a polar group-containing monomer was 100%.
- the homopolymer was also detected in the analytical power of the extract. First, it was confirmed that 100% of the added monomer was introduced into the natural rubber molecule. Therefore, the produced modified natural rubber is 2-Burpyridine 0.5% modified natural rubber.
- the rubber composition having the composition shown in Table 2 was evaluated as follows, and the results are shown in Table 2.
- Modified natural rubber A 2-Burpyridine produced in Production Example 2 0.5% modified natural rubber
- Modified natural rubber B Gamma-methacryloxypropyltrimethoxysilane produced in Production Example 3 5% modified natural rubber
- Carbon black “Asahi # 70—NP” manufactured by N330 Asahi Carbon Co., Ltd.
- Vulcanization accelerator Sanshin Igaku Kogyo Co., Ltd. “Suncellor NS—G” (N (tert-butyl) -2-benzothiazolesulfenamide)
- a rubber composition vulcanized under vulcanization conditions 160 ° C x 20 minutes was punched into a dumbbell shape, and a sample with a 5mm pre-crack in the center was 80 ° C with a chuck distance of 20 ° using a fatigue tester.
- a stroke of 7 Hz at a constant stress of mm was given, and the number of times until complete fracture was shown as an index, with the case of Comparative Example 7 being 100. Larger values indicate longer life and better crack growth resistance.
- a rubber composition vulcanized under vulcanization conditions 160 ° CX 14 minutes), using a Toyo Seiki spectrometer (dynamic viscoelasticity tester), initial load 160g, frequency 50Hz, strain 1 It was measured at 0% and a measurement temperature of 23 ° C., and the case of Comparative Example 7 was taken as 100 and displayed as an index. The larger tan S, the lower the loss.
- the rolling resistance of the tire (size 185 / 70R1 4) was measured with a drum using the rubber composition as a ply-coating rubber. This value is large The lower the rolling resistance, the better the rolling resistance.
- Example 6 in which part of the carbon black was replaced with silica, the grafted alkoxysilane strengthened the bond between the natural rubber and the silica, and as a result, the durability was significantly higher than in Comparative Example 9. Improved.
- the present invention is based on Japanese Patent Application 2004-346506 and Japanese Patent Application 2004-346507, each filed on November 30, 2004, the entire contents of which are incorporated by reference.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP05806788A EP1818186A4 (en) | 2004-11-30 | 2005-11-18 | PNEUMATIC |
US11/798,841 US20070221310A1 (en) | 2004-11-30 | 2007-05-17 | Pneumatic tire |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004346507A JP2006152157A (ja) | 2004-11-30 | 2004-11-30 | 空気入りタイヤ |
JP2004-346506 | 2004-11-30 | ||
JP2004346506A JP4617853B2 (ja) | 2004-11-30 | 2004-11-30 | 空気入りタイヤ |
JP2004-346507 | 2004-11-30 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/798,841 Continuation US20070221310A1 (en) | 2004-11-30 | 2007-05-17 | Pneumatic tire |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2006059503A1 true WO2006059503A1 (ja) | 2006-06-08 |
Family
ID=36564938
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2005/021251 WO2006059503A1 (ja) | 2004-11-30 | 2005-11-18 | 空気入りタイヤ |
Country Status (3)
Country | Link |
---|---|
US (1) | US20070221310A1 (ja) |
EP (1) | EP1818186A4 (ja) |
WO (1) | WO2006059503A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2010055877A1 (ja) * | 2008-11-12 | 2010-05-20 | 株式会社ブリヂストン | 接着剤組成物 |
EP2067819A4 (en) * | 2006-09-29 | 2011-11-23 | Bridgestone Corp | RUBBER COMPOSITION FOR SIDE RUBBER AND RADIAL LOADS FOR HEAVY LOADS USED THEREOF |
Families Citing this family (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8609252B2 (en) | 2007-12-27 | 2013-12-17 | Bridgestone Corporation | Rubber composition |
GB0812185D0 (en) | 2008-07-03 | 2008-08-13 | Dow Corning | Polymers modified by silanes |
GB0812186D0 (en) | 2008-07-03 | 2008-08-13 | Dow Corning | Modified polyolefins |
WO2010125124A1 (en) * | 2009-04-30 | 2010-11-04 | Dow Corning Corporation | Elastomer compositions modified by silanes |
GB201000117D0 (en) | 2010-01-06 | 2010-02-17 | Dow Corning | Organopolysiloxanes containing an unsaturated group |
GB201000121D0 (en) | 2010-01-06 | 2010-02-17 | Dow Corning | Modified polyolefins |
GB201000120D0 (en) | 2010-01-06 | 2010-02-17 | Dow Corning | Process for forming crosslinked and branched polymers |
GB201000137D0 (en) * | 2010-01-06 | 2010-02-24 | Dow Corning | Modified diene elastomers |
FR2966829B1 (fr) * | 2010-11-03 | 2012-11-16 | Rhodia Operations | Utilisation d'une silice precipitee contenant de l'aluminium et ayant une distribution poreuse particuliere et de 3-acryloxy-propyltriethoxysilane dans une compostion d'elastomere(s) isoprenique(s) |
US20120073720A1 (en) * | 2010-09-28 | 2012-03-29 | The Goodyear Tire & Rubber Company | Wire coat compositions for rubber articles |
FR2966833B1 (fr) * | 2010-11-03 | 2012-11-16 | Rhodia Operations | Utilisation d'une silice precipitee sous forme de granules, ayant une distribution poreuse particuliere, et de 3-acryloxy-propyltriethoxysilane dans une composition d'elastomere(s) isoprenique(s) |
FR2966830B1 (fr) * | 2010-11-03 | 2012-11-16 | Rhodia Operations | Utilisation d'une silice precipitee contenant de l'aluminium, d'une silice precipitee et de 3-acryloxy-propyltriethoxysilane dans une composition d'elastomere(s) isoprenique(s) |
FR2966831B1 (fr) * | 2010-11-03 | 2012-12-14 | Rhodia Operations | Utilisation d'une silice a distribution granulometrique et/ou repartition poreuse particulieres et de 3-acryloxy-propyltriethoxysilane dans une composition d'elastomere(s) isoprenique(s) |
FR2966832B1 (fr) * | 2010-11-03 | 2012-12-14 | Rhodia Operations | Utilisation d'une silice precipitee a surface specifique elevee et de 3-acryloxy-propyltriehoxysilane dans une composition d'elastomere(s) isoprenique(s) |
CN102363648A (zh) * | 2011-06-29 | 2012-02-29 | 双钱集团(如皋)轮胎有限公司 | 一种高粘合强度的橡胶带束层 |
CN104086937A (zh) * | 2014-07-02 | 2014-10-08 | 安徽宁国尚鼎橡塑制品有限公司 | 一种减震橡胶组合物 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63203404A (ja) * | 1987-02-20 | 1988-08-23 | Yokohama Rubber Co Ltd:The | ラジアルタイヤ |
JPH0655665A (ja) * | 1992-08-11 | 1994-03-01 | Yokohama Rubber Co Ltd:The | 空気入りラジアルタイヤ |
JPH0790007A (ja) * | 1993-09-20 | 1995-04-04 | Sumitomo Rubber Ind Ltd | シラン変性ジエンゴム、加硫ゴム組成物およびシラン変性ジエンゴムの製造方法 |
JPH083368A (ja) * | 1994-06-17 | 1996-01-09 | Ube Ind Ltd | ゴムチェーファー用組成物 |
JPH10181305A (ja) * | 1996-12-26 | 1998-07-07 | Yokohama Rubber Co Ltd:The | 空気入りタイヤ |
JP2000026661A (ja) * | 1998-06-09 | 2000-01-25 | Pirelli Pneumatici Spa | シリカ強化タイヤ組成物 |
JP2004284375A (ja) * | 2003-03-19 | 2004-10-14 | Bridgestone Corp | 高速重荷重用空気入りラジアルタイヤ |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3272676A (en) * | 1961-09-14 | 1966-09-13 | Teikoku Jinzo Kenshi Kk | Method of effecting the adhesion of polyester materials to rubbers |
US4898223A (en) * | 1989-01-30 | 1990-02-06 | The Goodyear Tire & Rubber Company | Stiff rubber composition and articles having components thereof |
US5253691A (en) * | 1992-01-13 | 1993-10-19 | The Goodyear Tire & Rubber Company | Tire having specified belt rubber composition |
US6848487B2 (en) * | 2002-12-19 | 2005-02-01 | The Goodyear Tire & Rubber Company | Pneumatic tire having a rubber component containing a rubber gel and starch composite |
MY146353A (en) * | 2003-06-02 | 2012-08-15 | Bridgestone Corp | Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire |
-
2005
- 2005-11-18 WO PCT/JP2005/021251 patent/WO2006059503A1/ja active Application Filing
- 2005-11-18 EP EP05806788A patent/EP1818186A4/en not_active Withdrawn
-
2007
- 2007-05-17 US US11/798,841 patent/US20070221310A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63203404A (ja) * | 1987-02-20 | 1988-08-23 | Yokohama Rubber Co Ltd:The | ラジアルタイヤ |
JPH0655665A (ja) * | 1992-08-11 | 1994-03-01 | Yokohama Rubber Co Ltd:The | 空気入りラジアルタイヤ |
JPH0790007A (ja) * | 1993-09-20 | 1995-04-04 | Sumitomo Rubber Ind Ltd | シラン変性ジエンゴム、加硫ゴム組成物およびシラン変性ジエンゴムの製造方法 |
JPH083368A (ja) * | 1994-06-17 | 1996-01-09 | Ube Ind Ltd | ゴムチェーファー用組成物 |
JPH10181305A (ja) * | 1996-12-26 | 1998-07-07 | Yokohama Rubber Co Ltd:The | 空気入りタイヤ |
JP2000026661A (ja) * | 1998-06-09 | 2000-01-25 | Pirelli Pneumatici Spa | シリカ強化タイヤ組成物 |
JP2004284375A (ja) * | 2003-03-19 | 2004-10-14 | Bridgestone Corp | 高速重荷重用空気入りラジアルタイヤ |
Non-Patent Citations (1)
Title |
---|
See also references of EP1818186A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2067819A4 (en) * | 2006-09-29 | 2011-11-23 | Bridgestone Corp | RUBBER COMPOSITION FOR SIDE RUBBER AND RADIAL LOADS FOR HEAVY LOADS USED THEREOF |
WO2010055877A1 (ja) * | 2008-11-12 | 2010-05-20 | 株式会社ブリヂストン | 接着剤組成物 |
Also Published As
Publication number | Publication date |
---|---|
EP1818186A1 (en) | 2007-08-15 |
US20070221310A1 (en) | 2007-09-27 |
EP1818186A4 (en) | 2009-04-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2006059503A1 (ja) | 空気入りタイヤ | |
JP4518750B2 (ja) | ゴム組成物および空気入りタイヤ | |
WO2007066689A1 (ja) | ゴム組成物及びそれを用いたタイヤ | |
US9132697B2 (en) | Modified natural rubber or modified natural rubber latex, and rubber composition and pneumatic tire | |
WO2010071106A1 (ja) | 天然ゴム、その製造方法、ゴム組成物およびこれを用いた空気入りタイヤ、改質天然ゴムおよびその製造方法、並びに、トレッドまたはカーカスコード被覆用ゴム組成物およびこれらを用いた空気入りタイヤ | |
US9181378B2 (en) | Modified natural rubber and method of manufacturing the same, rubber composition and tire | |
KR19980703384A (ko) | 디엔계 고무 조성물 | |
JP4925592B2 (ja) | 変性天然ゴム、及びそれを用いたゴム組成物、タイヤ | |
EP1081162A1 (en) | Conjugated diene rubber, process for producing the same, and rubber composition | |
JP4302547B2 (ja) | 変性天然ゴムラテックス、変性天然ゴム及びそれらの製造方法 | |
JP4617853B2 (ja) | 空気入りタイヤ | |
JP5823803B2 (ja) | 変性天然ゴムラテックス及びその製造方法、並びに、変性天然ゴム、ゴム組成物、及びタイヤ | |
CN101421120A (zh) | 充气轮胎 | |
JP5002162B2 (ja) | 変性天然ゴム、並びにそれを用いたゴム組成物及びタイヤ | |
JP5002161B2 (ja) | 変性天然ゴム及びその製造方法、並びにそれを用いたゴム組成物及びタイヤ | |
JP2008184572A (ja) | 変性水添天然ゴムの製造方法、変性水添天然ゴム、ゴム組成物及びそれを用いた空気入りタイヤ | |
JP2006151259A (ja) | 空気入りタイヤ | |
JP6220494B2 (ja) | 変性天然ゴムの製造方法、変性天然ゴム、ゴム組成物、及び、タイヤ | |
EP2716701A1 (en) | Rubber composition and tire using same | |
JP4665493B2 (ja) | ゴム組成物及び空気入りタイヤ | |
JP5019752B2 (ja) | 変性天然ゴム及びその製造方法、並びにゴム組成物及びタイヤ | |
JP2013104055A (ja) | 変性天然ゴム及びその製造方法、並びに、ゴム組成物及びタイヤ | |
JP2012171486A (ja) | 空気入りタイヤ | |
JP2006151261A (ja) | 空気入りタイヤ |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 200580041097.X Country of ref document: CN |
|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS KE KG KM KN KP KR KZ LC LK LR LS LT LU LV LY MA MD MG MK MN MW MX MZ NA NG NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SM SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GM KE LS MW MZ NA SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LT LU LV MC NL PL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2005806788 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 11798841 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWP | Wipo information: published in national office |
Ref document number: 2005806788 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 11798841 Country of ref document: US |