CN102108142A - Rubber composition for tire tread and tire manufactured using composition - Google Patents
Rubber composition for tire tread and tire manufactured using composition Download PDFInfo
- Publication number
- CN102108142A CN102108142A CN201010563338XA CN201010563338A CN102108142A CN 102108142 A CN102108142 A CN 102108142A CN 201010563338X A CN201010563338X A CN 201010563338XA CN 201010563338 A CN201010563338 A CN 201010563338A CN 102108142 A CN102108142 A CN 102108142A
- Authority
- CN
- China
- Prior art keywords
- mentioned
- rubber
- rubber composition
- weight
- tire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- 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
- B60C1/0016—Compositions of the tread
-
- 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
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- 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
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)
Abstract
The invention provides a rubber composition for a tire tread and a tire manufactured using the rubber composition, and the rubber composition comprises 100 parts by weight of rubber raw materials which contain 70-90 parts by weight of solution polymerized styrene-butadiene rubbers (S-SBR) with the styrene content of 20-30 wt% and the content of the vinyl group contained in butadiene of 50-60 wt%; 10-30 parts by weight of butadiene rubbers (BR); and 60-90 parts by weight of silicon dioxide. The end of the molecule of the solution polymerized styrene-butadiene rubber is modified to be alkoxy silane, and the molecules are coupled by silicon. The rubber composition for a tire tread reduces hysteresis loss and maximizes the performance of low fuel consumption, and the reduced braking performance as a result of the maximization of the performance of low fuel consumption becomes excellent; the rubber composition for a tire tread also improves the processability in an unvulcanized state, the braking performance in a vulcanized state, the abrasion resistance and the revolving resistance.
Description
Technical field
The tire that the present invention relates to rubber composition for tire tread and utilize said composition to make, particularly, relate to the excellent processability under sulfided state not, and the tire that has improved the rubber composition for tire tread of braking, wear resistance and low burnup performance simultaneously and utilized said composition to make.
Background technology
In recent years, along with the high performance of passenger car, human consumers have also proposed the requirement of high performance to tire, particularly, demand to the tire that has wear resistance, handling, driving, wetland braking ability and low burnup performance simultaneously concurrently causes the application of active research exploitation novel material.In order to develop the tire that has above-mentioned wear resistance, handling, driving, wetland braking ability and low burnup performance simultaneously concurrently, particularly in the material field, carrying out a large amount of research.
Generally speaking,, reduce the usage quantity of reinforcing filler, thereby reduce the interaction between toughener and the toughener, so that reduce hysteresis loss in order to reduce the rotational resistance relevant with the burnup performance of tire.
Yet, in this technology, exist content to reduce, as the braking ability of the key property of tire tread and the shortcoming that control stability can reduce along with enhancing property weighting agent.
As mentioned above, in the developing material technology of existing tire, if improve the wear resisting property and the burnup performance of tire, then the situation that braking ability reduces on the contrary can take place; When improving tire braking performance, then can be unfavorable for the burnup performance or reduce the situation that wear resisting property reduces.So, with regard to the various performances of tire, if improve wherein a kind of performance, the phenomenon that other performances reduce then can take place, therefore, when needing exploitation to improve a kind of performance, the reduction of other performances minimizes as far as possible, perhaps two kinds of technology that performance improves simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of rubber composition for tire tread, make under sulfided state not, processing characteristics is good, also improves braking, wear resistance and low burnup simultaneously.
Another object of the present invention is to, the tire that uses above-mentioned rubber composition for tire tread to make is provided.
To achieve these goals, the rubber composition for tire tread that one embodiment of the invention relate to, comprise: the crude rubber of 100 weight parts, it contains: the solution polymerization type styrene butadiene rubbers (S-SBR) of 70 to 90 weight parts, wherein, cinnamic content is 20 to 30 weight %, and the contents of ethylene that divinyl comprises is 50 to 60 weight %; Divinyl rubber (BR) with 10 to 30 weight parts; And the silicon-dioxide of 60 to 90 weight parts; Molecular end in the above-mentioned solution polymerization type styrene butadiene rubbers is modified as organoalkoxysilane, passes through the mutual coupling of silicon between the molecule.
Preferably, the nitrogen adsorption specific surface area of above-mentioned silicon-dioxide is 150 to 185m
2/ g, cetyl trimethylammonium bromide (CTAB) adsorption specific surface area is 150 to 170m
2/ g.
According to another embodiment of the present invention, provide a kind of tire that uses above-mentioned rubber composition for tire tread to make.
Below, describe the present invention in detail.
Above-mentioned rubber composition for tire tread comprises: the crude rubber that contains styrene butadiene rubbers and divinyl rubber; And silicon-dioxide.
For the rotational resistance performance of the best, above-mentioned styrene butadiene rubbers is preferably used 70 to 90 weight parts.When the content of above-mentioned styrene butadiene rubbers surpassed 90 weight parts, wear resisting property can reduce; When containing quantity not sufficient 70 weight parts, rotational resistance characteristic and braking ability can reduce.
Above-mentioned styrene butadiene rubbers comprises that cinnamic content is that the contents of ethylene that 20 to 30 weight %, divinyl are comprised is the solution polymerization type styrene butadiene rubbers of 50 to 60 weight %.When using cinnamic content is under the situation of above-mentioned styrene butadiene rubbers of 20 to 30 weight %, owing to be beneficial to the microtexture of rotational resistance, makes low burnup excellent property.
Above-mentioned styrene butadiene rubbers, missible oil aggretion type styrene butadiene rubbers (Emulsion-polymerized Styrene Butadiene Rubber is arranged, E-SBR) and solution polymerization type styrene butadiene rubbers (Solution-polymerized Styrene Butadiene Rubber, S-SBR) two kinds.
Generally, above-mentioned solution polymerization type styrene butadiene rubbers can obtain by continous way method and batch process manufacturing.Particularly, above-mentioned solution polymerization type styrene butadiene rubbers can be by the batch process manufacturing.Solution polymerization type styrene butadiene rubbers by above-mentioned continous way method manufacturing, compare with solution polymerization type styrene butadiene rubbers by above-mentioned batch process manufacturing, though excellent processability some, but a large amount of low molecular weight substances can cause producing a large amount of hysteresis losses, therefore, be unfavorable for low burnup performance.On the contrary, solution polymerization type styrene butadiene rubbers by the batch process manufacturing, because its molecular weight distribution degree (MWD) is 1.3 to 1.5, therefore, with compare by the styrene butadiene rubbers of continous way method manufacturing, present narrower molecular weight distribution, help rotational resistance performance and low burnup performance.
Molecular end in the above-mentioned solution polymerization type styrene butadiene rubbers is modified as organoalkoxysilane, can pass through silicon coupling (coupling) between the molecule.
Molecular end is modified as in the solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane, can improve the dispersiveness of silicon-dioxide, and the interaction between enhancing silicon-dioxide and rubber, improve the low burnup performance of rubber, and, linked reaction by silicon connects each molecule, produces the molecule terminal number of reason thereby reduce as lagging behind, and can make low burnup performance maximization.In addition, its processibility and low burnup performance are also good.
Above-mentioned organoalkoxysilane refers to the silane compound that contains alkoxyl group.Be modified as in the solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane in molecular end, the organoalkoxysilane of the molecular end that is modified can be represented with following Chemical formula 1.
[Chemical formula 1]
In the above-mentioned Chemical formula 1,
Above-mentioned R
1And R
3Be respectively independently from being that 1 to 15 alkyl, charcoal prime number are that 1 to 15 special-shaped alkyl, carbon element number are that 3 to 15 ring-like alkyl, carbon element number are that 3 to 15 different ring-like alkyl, carbon element number are any that select 1 to 15 alkoxyl group and their group that constitutes by hydrogen, halo atom, charcoal prime number, preferably from being that 1 to 10 alkyl, carbon element number are that 1 to 10 special-shaped alkyl, carbon element number are any that select 1 to 10 alkoxyl group and their group that constitutes by hydrogen, halo atom, charcoal prime number.
Above-mentioned R
2Be from being that 1 to 15 alkyl, charcoal prime number are that 1 to 15 special-shaped alkyl, carbon element number are that 3 to 15 ring-like alkyl, carbon element number are any that select 3 to 15 shaped rings alkyl and their group that constitutes by hydrogen, halo atom, charcoal prime number, preferably from being that 1 to 10 alkyl, carbon element number are any of 1 to 10 special-shaped alkyl and their group selection that constitutes by hydrogen, halo element, carbon element number.
Above-mentioned special-shaped alkyl is meant the carbon atom in the alkyl is replaced to 1 to 3 different (hetero) atom selecting that from the group that is made of above-mentioned N, O, S and P above-mentioned shaped rings alkyl is meant the carbon atom in the ring-like alkyl is replaced to 1 to 3 the exotic atom of selecting from the group that is made of above-mentioned N, O, S and P.Above-mentioned halogen atom can be any that select from the group that is made of fluorine, chlorine, bromine, iodine.
Particularly, molecular end is modified as in the solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane, and molecular end can be modified as from by any alkoxysilane compound containing trialkylsilyl group in molecular structure of selecting propyl trimethoxy silicane, propyl-triethoxysilicane, N-hexyl Trimethoxy silane, methyl dimethoxysilane, benzene Trimethoxy silane, Ethenylbenzene methyl-amino methyl-aminopropyl-triethoxyl silane, sulfydryl Trimethoxy silane and their group that constitutes.
Molecular end is modified as the solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane, butadiene type monomer, vinyl monomer and organoalkoxysilane can be carried out polymerization in non-active solvent and makes.
The monomeric representative of above-mentioned butadiene type is a 1,3-butadiene, but is not limited to this; The representative of vinyl monomer is a vinylbenzene, but the present invention is not limited to this.Above-mentioned non-active solvent can be from by select benzene,toluene,xylene, pentane, hexane, heptane, different oxane, hexanaphthene and their group that constitutes any, but be not limited thereto, if non-active solvents such as aliphatics carbonization hydrogen, alicyclic hydrocarbon, aromatic series hydrocarbon can use.
Be modified as in the manufacturing of solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane in molecular end, can use polymerization starter, above-mentioned polymerization starter can use basic metal, alkaline-earth metal etc., can also use from by select lithium, barium and their group that constitutes any, but be not limited thereto.
Above-mentioned polyreaction can be carried out under 20 to 120 ℃ continuously or discontinuously.
Molecular end is modified as in the solution polymerization type styrene butadiene rubbers of above-mentioned organoalkoxysilane, can pass through the mutual coupling of silicon between the molecule.
The solution polymerization type styrene butadiene rubbers that makes molecular end be modified as above-mentioned organoalkoxysilane is carried out the link coupled method by silicon, can adopt the known method of the technical field of the invention to carry out, but be not limited to ad hoc approach of the present invention.
The solution polymerization type styrene butadiene rubbers that makes molecular end be modified as above-mentioned organoalkoxysilane is carried out the link coupled method by silicon, can be following method: after in the mixing solutions of vinylbenzene and divinyl, adding the polymerization starter of dual anionic form, carry out polymerization while stirring, the salinization tin that adds then as coupling agent stirs as the agent that terminates again, at this moment, in the polymeric molecular end of styrene butadiene, have the reaction of reactive free radical and salinization tin, make multiple polymers carry out coupling as media with tin.
For above-mentioned divinyl rubber, so long as the divinyl rubber that uses in the rubber composition for tire just can use.The content of above-mentioned divinyl rubber can be 10 to 30 weight parts, when the content that uses above-mentioned divinyl rubber surpasses 30 weight parts, the ratio of the divinyl rubber that rubbery intensity is more weak uprises, so braking may reduce, when use contained quantity not sufficient 10 weight parts, the problem that wear resistance reduces can take place.
Above-mentioned divinyl rubber preferably uses the divinyl rubber that does not contain oils.When above-mentioned divinyl rubber oil-containing time-like not, have low burnup and the favourable effect of processibility.
Above-mentioned rubber composition for tire tread contains silicon-dioxide as enhancing property weighting agent.
In order to obtain realizing the tread rubber composition of the object of the invention, it is 150 to 185m that above-mentioned silicon-dioxide preferably uses the nitrogen adsorption specific surface area
2(cetyltrimenthyl ammonium bromide, CTAB) adsorption specific surface area is 150 to 170m for/g, cetyl trimethylammonium bromide
2The silicon-dioxide of/g, more preferably using the nitrogen adsorption specific surface area is 160 to 185m
2/ g, cetyl trimethylammonium bromide (CTAB) adsorption specific surface area are 155 to 165m
2The silicon-dioxide of/g.
With respect to the crude rubber of 100 weight parts, can use the above-mentioned silicon-dioxide of 60 to 90 weight parts, when the content of above-mentioned silicon-dioxide surpassed 90 weight parts, the rotational resistance performance can reduce; When content during, unfavorable to wear resistance less than 60 weight parts.
Above-mentioned silicon-dioxide can use all silicon-dioxide by wet type method for making or the preparation of dry type method for making, as commercially available product, can use Ultrasil VN2 (manufacturing of Degussa company), Ultrasil VN3 (manufacturing of Degussa company) etc., but be not limited thereto.
In order to improve the dispersiveness of above-mentioned silicon-dioxide, can further contain coupling agent in the above-mentioned rubber composition for tire tread.
As above-mentioned coupling agent, can use from being that coupling agent, ethene base system coupling agent, amino are that coupling agent, glycidoxy are that coupling agent, nitro are that coupling agent, chloro are that coupling agent, methacryloyl are any that select coupling agent and the group that constitutes thereof by sulfide-based coupling agent, sulfydryl.
Above-mentioned sulfide-based coupling agent can be from by two [3-(triethoxysilicane) propyl group]-tetrasulfides; two [2-(triethoxysilicane) ethyl]-tetrasulfides; two [4-(triethoxysilicane) butyl]-tetrasulfides; two [3-(trimethoxy silicon) propyl group]-tetrasulfides; two [2-(trimethoxy silicon) ethyl]-tetrasulfides; two [4-(trimethoxy silicon) butyl]-tetrasulfides; two [3-(triethoxysilicane) propyl group]-trisulphides; two [2-(triethoxysilicane) ethyl]-trisulphides; two [4-(triethoxysilicane) butyl]-trisulphides; two [3-(trimethoxy silicon) propyl group]-trisulphides; two [2-(trimethoxy silicon) ethyl]-trisulphides; two [4-(trimethoxy silicon) butyl]-trisulphides; two [3-(triethoxysilicane) propyl group]-disulphide; two [2-(triethoxysilicane) ethyl]-disulphide; two [4-(triethoxysilicane) butyl]-disulphide; two [3-(trimethoxy silicon) propyl group]-disulphide; two [2-(trimethoxy silicon) ethyl]-disulphide; two [4-(trimethoxy silicon) butyl]-disulphide; 3-trimethoxy silicon propyl group-N; N-dimethyl thiocarbamoyl tetrasulfide; 3-triethoxysilylpropyl-N; N-dimethyl thiocarbamoyl tetrasulfide; 2-triethoxy silica ethyl-N; N-dimethyl thiocarbamoyl tetrasulfide; 2-trimethoxy silica ethyl-N, N-dimethyl thiocarbamoyl tetrasulfide; 3-trimethoxy silicon propyl group benzothiazole tetrasulfide; 3-triethoxysilylpropyl benzothiazole tetrasulfide; 3-trimethoxy silicon propyl methyl acid esters list sulfide; any one that select in 3-trimethoxy silicon propyl methyl acid esters list sulfide and the group that constitutes thereof.
Above-mentioned sulfydryl be coupling agent can be from by select (3-sulfydryl propyl group) Trimethoxy silane, (3-sulfydryl propyl group) triethoxyl silane, (2-mercaptoethyl) Trimethoxy silane, (2-mercaptoethyl) triethoxyl silane and the group that constitutes thereof any.Above-mentioned ethene base system coupling agent can be from by select Ethoxysilane, vinyltrimethoxy silane and the group that constitutes thereof any.Above-mentioned amino be coupling agent can be from by select 3-aminopropyltriethoxywerene werene, 3-TSL 8330,3-(2-amino-ethyl) aminopropyltriethoxywerene werene, 3-(2-amino-ethyl) TSL 8330 and the group that constitutes thereof any.
Above-mentioned glycidoxy be coupling agent can be from by select γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, γ-glycidoxy propyl group methyl dimethoxysilane and the group that constitutes thereof any.Above-mentioned nitro be coupling agent can be from by select 3-nitro propyl trimethoxy silicane, 3-nitro propyl-triethoxysilicane and the group that constitutes thereof any.Above-mentioned chlorine be coupling agent can be from by select 3-r-chloropropyl trimethoxyl silane, 3-chloropropyl triethoxysilane, 2-chloroethyl Trimethoxy silane, 2-chloroethyl triethoxyl silane and the group that constitutes thereof any.
Above-mentioned methacryloyl be silane compound can be from by select (γ-methacryloyl propyl group) Trimethoxy silane, (γ-methacryloyl propyl group) methyl dimethoxysilane, (γ-methacryloyl propyl group) dimethyl methyl TMOS and the group that constitutes thereof any.
With respect to the crude rubber of 100 weight parts, can contain the above-mentioned coupling agent of 4.8 to 7.2 weight parts.When the content of above-mentioned coupling agent during less than 4.8 weight parts, insufficient with the reaction of silicon-dioxide, cause the processibility of rubber to reduce, perhaps low burnup performance reduces; When content surpassed 7.2 weight parts, the interaction between silicon-dioxide and the rubber was strong excessively, though low burnup excellent property, braking ability may reduce a lot.
Above-mentioned rubber composition for tire tread can also comprise various additives such as the vulcanizing agent that optionally appends, vulcanization accelerator, vulcanization accelerator additive, antiaging agent, tenderizer.For above-mentioned various additives, so long as the additive that often uses just can use in the technical field of the invention, its content does not limit at this especially according to the proportioning decision of using in the common rubber composition for tire tread.
Above-mentioned vulcanizing agent can use metal oxides such as sulphur class vulcanizing agent, organo-peroxide, resin cure agent, magnesium oxide.
As above-mentioned sulphur class vulcanizing agent, can use sulphur powder (S), insoluble sulfur (S), precipitation sulphur (S), the inorganic sulphide agent such as (colloid) of colloid sulphur, and tetramethyl-thiuram disulfide (tetramethyl thiuram disulfide, TMTD), tetraethylthiuram disulfide (tetraethyl thiuram disulfide, TETD), dithio morpholine organic sulfurizing agents such as (dithiodimorpholine).Particularly, above-mentioned sulfur vulcanizing agent can use the vulcanizing agent that can prepare primary sulfur or sulphur, for example curing amine (amine disulfide), polymer sulphur etc.
Above-mentioned organo-peroxide can use from by benzoyl peroxide, dicumyl peroxide, ditertiary butyl peroxide, the tert-butyl peroxide diisopropylbenzyl, methylethyl ketone peroxide, Cumene Hydroperoxide 80,2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 2,5-dimethyl-2,5-two (benzoyl peroxy) hexane, 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, 1, two (t-butylperoxy propyl group) benzene of 3-, di-tert-butyl peroxide-diisopropylbenzene(DIPB), t-butylperoxy benzene, peroxidation 2, the 4-dichloro-benzoyl, 1,1-di-t-butyl peroxy-3,3, the 5-trimethicone, 4, any that select in 4-di-tert-butyl peroxide n-butyl pentanoate and the group that constitutes thereof.
Comprise the above-mentioned vulcanizing agent of 0.5 to 2.5 weight part with respect to the above-mentioned raw materials rubber of 100 weight parts, this can realize preferable cure efficiency, makes crude rubber insensitive to heat, and stable chemical performance, is preferred content therefore.
Above-mentioned vulcanization accelerator is meant the promotor (accelerator) that promotes vulcanization rate or promote delayed action at initial sulfurating stage.
As above-mentioned vulcanization accelerator, can use from by select sulfenamide, thiazoles, thiocarbamyl class, Thiourea, guanidine class, dithiocarbamate(s), aldehyde amines, aldehyde ammonia class, imidazolines, xanthogenic acid salt and the group that constitutes thereof any.
As above-mentioned sulfenamide vulcanization accelerator, for example can use from by N cyclohexyl 2 benzothiazole sulfenamide (CBS), N tert butyl benzothiazole 2 sulfenamide (TBBS), N, N-dicyclohexyl-2-[4-morpholinodithio sulphenamide, N oxydiethylene 2 benzothiazole sulfenamide, N, any sulphenamide compounds of selecting in N-di-isopropyl-2-[4-morpholinodithio sulphenamide and the group that constitutes thereof.
As above-mentioned thiazoles vulcanization accelerator, for example can use from sodium salt, the zinc salt of 2-mercaptobenzothiazole, the mantoquita of 2-mercaptobenzothiazole, the cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2 by 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), 2-mercaptobenzothiazole, the 4-dinitrophenyl) any thiazole compound of selecting in mercaptobenzothiazole, 2-(2,6-diethyl-4-morpholinothio) benzothiazole and the group that constitutes thereof.
As above-mentioned thiocarbamyl class vulcanization accelerator, for example can use from by tetramethyl-thiocarbamyl disulphide (TMTD), tetraethyl-thiocarbamyl disulphide, tetramethyl-thiocarbamyl list sulfide, two pentylidene thiocarbamyl disulphide, two pentylidene thiocarbamyl disulphide, two pentylidene thiocarbamyl tetrasulfides, two pentylidene thiocarbamyl hexasulfides, tetrabutyl thiocarbamyl disulphide, any thiocarbamyl compounds of selecting in pentylidene thiocarbamyl tetrasulfide and the group that constitutes thereof.
As above-mentioned Thiourea vulcanization accelerator, for example can use from by any thiourea of selecting thiocarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, di-o-tolyl-thiourea and the group that constitutes thereof.
As above-mentioned guanidine class vulcanization accelerator, for example can use from by the guanidine compound of selecting diphenylguanidine, di-o-tolylguanidine, triphenyl guanidine, di-o-tolylguanidine, diphenylguanidine phthalic ester and the group that constitutes thereof.
As above-mentioned dithiocar-bamate vulcanization accelerator, for example can use from by zinc-ethylphenyl dithiocarbamate, the butyl phenyl zinc dithiocarbamate, Sodium dimethyldithiocarbamate 40min, ziram, zinc diethyldithiocarbamate, zinc dibutyl dithiocarbamate, zinc diamyldithiocarbamate, the dipropyl zinc dithiocarbamate, the complex compound of zinc pentamethylene dithiocarbamate and piperidines, hexadecyl sec.-propyl zinc dithiocarbamate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyldithiocarbamate, Thiocarb, pentamethylene dithiocarbamic acid piperidines, dimethyl dithiocarbamic acid arsenic, tellurium diethyl dithiocarbamate, any dithiocarbamate(s) compound of selecting in lead diamyldithiocarbamate and the group that constitutes thereof.
As above-mentioned aldehyde amines or aldehyde ammonia class vulcanization accelerator, for example can use from by aldehyde amines or the aldehyde ammonia compounds selected acetaldehyde-aniline reaction product, butyraldehyde-aniline complex compound, hexamethylenetetramine, aldamine reaction product and the group that constitutes thereof.
As above-mentioned imidazolines vulcanization accelerator, for example can use imidazolines such as 2-mercaptoimidazoline, as above-mentioned xanthogenic acid salt vulcanization accelerator, for example can use xanthogenic acid compounds such as dibutyl xanthogenic acid zinc.
For by promoting that vulcanization rate makes the raising of productivity and the raising of rubber physical property reach maximization,, can contain the above-mentioned vulcanization accelerator of 0.5 to 4.0 weight part with respect to the above-mentioned raw materials rubber of 100 weight parts.
Above-mentioned vulcanization accelerator additive be with above-mentioned vulcanization accelerator and with and make the more abundant employed Synergist S-421 95 of facilitation effect, can use from by select mineral-type vulcanization accelerator additive, organic class vulcanization accelerator additive and the group that constitutes thereof any.
As above-mentioned mineral-type vulcanization accelerator additive, can use from by select zinc oxide (ZnO), charcoal acid zinc (zinc carbonate), magnesium oxide (MgO), plumbous oxide (lead oxide), potassium hydroxide and the group that constitutes thereof any.As above-mentioned organic class vulcanization accelerator additive, can use from by select stearic acid, Zinic stearas, palmitinic acid, linolic acid, oleic acid, lauric acid, DBAO dibutylammonium oleate (dibutyl ammonium oleate), their derivative and the group that constitutes thereof any.
Especially, as above-mentioned vulcanization accelerator additive, can use above-mentioned zinc oxide and above-mentioned stearic acid simultaneously, in this case, above-mentioned zinc oxide is dissolved in the above-mentioned stearic acid, form effective mixture (complex) with above-mentioned vulcanization accelerator, in vulcanization reaction, generate free sulphur, thus the crosslinking reaction of easy realization and rubber.
Use at the same time under above-mentioned zinc oxide and the above-mentioned stearic situation,,, can use 1 to 5 weight part and 0.5 to 3 weight part respectively with respect to the crude rubber of 100 weight parts in order to obtain the effect of preferable vulcanization accelerator additive.
The processibility of above-mentioned rubber composition for tire tread is good, so can not comprise tenderizer when mixed rubber, still, also can be included in conventional tyre with the tenderizer that uses in the rubber.
Process or reduce the hardness of vulcanized rubber in order to give plasticity-easily, can in rubber combination, add above-mentioned tenderizer rubber.Above-mentioned tenderizer can use from by select treated oil (Process oil), Vegetable oil lipoprotein and the group that constitutes thereof any, but the invention is not restricted to this.
As above-mentioned treated oil, can use from by select paraffin, naphthenic oil, fragrant same clan oil and the group that constitutes thereof any.
But, along with the raising of environmental consciousness in recent years, the content of recognizing the polycyclic aromatic hydrocarbons (Polycyclic Aromatic Hydrocarbons below is called " PAHs ") that contains in the above-mentioned aromatic oil is 3 weight % when above, and the possibility of bringing out cancer strengthens.Treated oil as above-mentioned tenderizer use, can preferably use with respect to whole above-mentioned treated oils, the total content of PAHs composition is that 3 weight % are following, dynamic viscosity aromatic component in (210 SUS), tenderizer more than 95 ℃ is that 27 to 37 weight % and alkanes composition are the treated oil of 38 to 58 weight % at 15 to 25 weight %, naphthenic composition.
Above-mentioned treated oil has following characteristic, and promptly, make cold property, the burnup excellent property of the tire tread comprise above-mentioned treated oil, the cancer that also is beneficial to PAHs is simultaneously brought out environmental protection factors such as possibility.
As above-mentioned Vegetable oil lipoprotein, can use from by select castor seeds oil, Oleum Gossypii semen, Semen Lini oil, mustard caul-fat, soybean oil, palm crude oil, Oleum Cocois, peanut oil, Pinus pumilio oil, Stockholm tar, pine tar, Semen Maydis oil, Rice pollard oil, Thistle oil, sesame oil, sweet oil, sunflower seed oil, palm-kernel oil, Camellia oil, Oenothera oil, Queensland nut oil, Thistle oil, tung oil and the group that constitutes thereof any.
Consider from improving the crude rubber processibility, preferably,, use the above-mentioned tenderizer of 20 to 40 weight parts with respect to the above-mentioned raw materials rubber of 100 weight parts.
Above-mentioned antiaging agent is the additive that uses for the chain reaction of the tire autoxidation of ending to be caused by oxygen.As above-mentioned antiaging agent, can use from by select amine, phenol, imidazoles, carbamic metal-salt and the group that constitutes thereof any.
As above-mentioned antiaging agent, can preferably use from by N-(1, the 3-dimethylbutyl)-(N-(1 for N '-diphenyl-para-phenylene diamine, 3-Dimethybutyl)-N-phenyl-p-phenylenedia mine, 6PPD), N-phenyl-N-sec.-propyl Ursol D (N-phenyl-N-i sopropyl-p-phenylenediamine, 3PPD), (2,2,4-trimethylammonium-1,2-dihydroquinoline polymkeric substance (Poly (2,2,4-trimethyl-1,2-dihydroquinol ine, RD) and the compound of selecting in the group that constitutes.
Above-mentioned antiaging agent is except having anti-aging effect, solubleness that need be in rubber is big, volatility is little, for rubber is not active, and do not hinder sulfuration etc., consider these conditions, with respect to the above-mentioned raw materials rubber of 100 weight parts, can contain the above-mentioned antiaging agent of 1 to 10 weight part.
Above-mentioned rubber composition for tire tread can use throughout the year, but preferably as using summer.Above-mentioned rubber composition for tire tread can improve when hanging down the burnup performance, keep braking ability and directional control performance, braking ability or wear resisting property in the snowfield that requires when using compared with winter, above-mentioned rubber composition for tire tread be more suitable for as summer with the braking on the burnup performance of the salient features of tire tread, the wet road surface, the directional control performance when running at high speed etc., have favourable effect.
The tire that another embodiment of the present invention relates to is to use above-mentioned rubber composition for tire tread to make.About utilizing above-mentioned rubber composition for tire tread to make the method for tire,, therefore, omit its detailed description in this manual so long as the method that tire in the past adopts in making is all applicable.
Rubber composition for tire tread of the present invention, reduced hysteresis loss, and low burnup performance is maximized, simultaneously, the braking ability that may reduce because of the maximization of low burnup performance also becomes good, improved processibility, the braking ability under the sulfided state, wear resistance and rotational resistance etc. under the sulfided state not simultaneously.
Embodiment
Below, describe embodiments of the invention in detail, make person of ordinary skill in the field of the present invention can go to realize it easily.But the present invention can show as various different shapes, the embodiment that is not limited to here illustrate.
[Production Example: the manufacturing of rubber composition for tire tread]
(embodiment and comparative example)
Utilize the composition shown in the following table 1, made the rubber composition for tire tread that following examples and comparative example relate to.The manufacture method of common tire tread rubber is adopted in the manufacturing of rubber composition for tire tread.
Table 1 (unit: weight part)
| Composition | Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 |
| E-SBR (1) | 80 | - | - | - | - |
| S-SBR (2) | - | 60 | - | 80 | 80 |
| S-SBR (3) | - | - | 80 | - | - |
| BR (4) | 20 | 40 | 20 | 20 | 20 |
| Silicon-dioxide (5) | 80 | 80 | 80 | 80 | - |
| Silicon-dioxide (6) | - | - | - | - | 80 |
| Coupling agent (7) | 6.4 | 6.4 | 6.4 | 6.4 | 6.4 |
| Zinc oxide | 3 | 3 | 3 | 3 | 3 |
| Stearic acid | 1 | 1 | 1 | 1 | 1 |
| Sulphur | 1.75 | 1.75 | 1.75 | 1.75 | 1.75 |
| Promotor (8 | 1 | 1 | 1 | 1 | 1 |
| Promotor (9) | 2 | 2 | 2 | 2 | 2 |
(1) E-SBR: letex polymerization styrene butadiene rubbers SBR1502;
(2) S-SBR: styrene content is that the contents of ethylene that 20 to 30 weight %, divinyl contain is 50 to 60 weight %, be modified as organoalkoxysilane by batch process manufacturing and molecular end, and intermolecular by Si link coupled solution polymerization type styrene butadiene rubbers (SBR);
(3) S-SBR: styrene content is that the contents of ethylene that 20 to 30 weight %, divinyl contain is 50 to 60 weight %, is modified as the solution polymerization type styrene butadiene rubbers (SBR) of organoalkoxysilane by batch process manufacturing and molecular end;
(4) BR: divinyl rubber;
(5) silicon-dioxide: the nitrogen adsorption specific surface area is 170m
2/ g, CTAB adsorption specific surface area are 160m
2The precipitated silica of/g;
(6) silicon-dioxide: the nitrogen adsorption specific surface area is 153m
2/ g, CTAB adsorption specific surface area are 154m
2The precipitated silica of/g;
(7) coupling agent: Si69, Degussa company makes;
(8) promotor: CBS (N-cyclohexyl-2-benzothiazole sulfenamide);
(9) promotor: DPG (vulkacit D);
[test example: measure the physical property that the tire tread of making is used rubber]
The tire tread that utilizes above-mentioned comparative example 1 to make to comparative example 3 and embodiment 1 and the embodiment 2 is measured physical property with rubber, and it be the results are shown in the following table 2.
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Embodiment 1 | Embodiment 2 | |
| Buddhist nun's viscosity not | 67 | 69 | 68 | 65 | 67 |
| Hardness (Shore A) | 66 | 65 | 64 | 65 | 64 |
| 300% modulus (Mpa) | 12.6 | 13.2 | 12.4 | 15.0 | 12.0 |
| Elongation (%) | 385 | 402 | 314 | 356 | 364 |
| Fastness to rubbing (Index) | 100 | 105 | 99 | 106 | 97 |
| 0℃tanδ | 0.304 | 0.284 | 0.299 | 0.342 | 0.354 |
| 60℃tanδ | 0.116 | 0.105 | 0.102 | 0.076 | 0.105 |
-Mo Ni viscosity (ML1+4 (125 ℃)) is measured according to ASTM standard D1646.
-hardness is measured according to DIN53505.
-300% modulus and elongation are according to the ISO37 canonical measure.
Elongation when-elongation is meant fracture is that the Strain value when quilt is broken in tensile testing machine with testing plate is measured with the method that % represents.
-fastness to rubbing is to use blue Berne wear testing machine (Lambourn abrasion tester) to measure.With comparative example 1 is that benchmark carries out exponentiate and represents.
-visco-elasticity is to use the RDS survey meter, has measured tan δ from 60 ℃ to 80 ℃ to 0.1% strain (strain) under the 10Hz frequency.
In the above-mentioned table 2, above-mentioned not Buddhist nun viscosity is the numerical value of the viscosity of expression unvulcanized rubber, and this value is low more, represents that then the processibility of unvulcanized rubber is good more.0 ℃ of tan δ represents braking ability, and this numerical value is big more, and then braking ability is better; 60 ℃ of tan δ represent the rotational resistance characteristic, and this numerical value is more little, then this more excellent performance.Above-mentioned hardness is represented control stability, and this numerical value is big more, and then control stability is good more.The numerical value of 300% modulus and elongation is big more, represents that its tensile properties is good more; The value of fastness to rubbing is high more, and then wear resisting property is better.
With reference to above-mentioned table 2, use with the content beyond the content range under the situation of comparative example 2 of S-SBR of the present invention, compare its braking ability with 2 with embodiment 1 and reduce; Under the situation of comparative example 3, compare with 2 with embodiment 1, elongation and braking ability show as lower.Embodiment 1 compares as can be seen with the comparative example 1 to 3 of conduct tread rubber composition in the past with 2 rubber, when having kept control stability, braking is good, and wear resisting property and rotational resistance characteristic are all very good, and fastness to rubbing, low burnup performance and braking ability are all very good.
More than; describe the preferred embodiments of the present invention in detail, but the claimed interest field of the present invention is not limited thereto, utilizes key concept of the present invention; by various distortion and the improvement that the person of ordinary skill in the field carries out, still belong to the interest field of request of the present invention.
Claims (3)
1. a rubber composition for tire tread is characterized in that, comprises:
The crude rubber of 100 weight parts, contain: the solution polymerization type styrene butadiene rubbers (S-SBR) of 70 to 90 weight parts, wherein, cinnamic content is 20 to 30 weight %, the contents of ethylene that divinyl comprises is 50 to 60 weight %; Divinyl rubber (BR) with 10 to 30 weight parts;
And the silicon-dioxide of 60 to 90 weight parts;
Molecular end in the above-mentioned solution polymerization type styrene butadiene rubbers is modified as organoalkoxysilane, passes through the mutual coupling of silicon between the molecule.
2. rubber composition for tire tread according to claim 1 is characterized in that,
The nitrogen adsorption specific surface area of above-mentioned silicon-dioxide is 150 to 185m
2/ g, cetyl trimethylammonium bromide (CTAB) adsorption specific surface area is 150 to 170m
2/ g.
3. tire that utilizes claim 1 or 2 described tire treads to make with composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2009-0130218 | 2009-12-23 | ||
| KR1020090130218A KR101140248B1 (en) | 2009-12-23 | 2009-12-23 | Tread rubber composition and tire manufactured by using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102108142A true CN102108142A (en) | 2011-06-29 |
| CN102108142B CN102108142B (en) | 2013-05-15 |
Family
ID=44172433
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010563338XA Expired - Fee Related CN102108142B (en) | 2009-12-23 | 2010-11-29 | Rubber composition for tire tread and tire manufactured using composition |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR101140248B1 (en) |
| CN (1) | CN102108142B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102634090A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tread rubber composition of fuel-efficient type semi-steel radial tire |
| CN103703072A (en) * | 2011-07-22 | 2014-04-02 | 住友橡胶工业株式会社 | Rubber composition for tread, and pneumatic tire |
| CN105670062A (en) * | 2016-01-27 | 2016-06-15 | 北京化工大学 | Wear-resistant tire tread rubber material with high wet skid resistance, low rolling resistance and high performance |
| CN107428202A (en) * | 2015-02-26 | 2017-12-01 | 横滨橡胶株式会社 | Pneumatic belt tire |
| CN107540900A (en) * | 2016-06-28 | 2018-01-05 | 住友橡胶工业株式会社 | Rubber composition and tire |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101395075B1 (en) * | 2011-12-29 | 2014-05-15 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
| KR101442213B1 (en) * | 2012-11-06 | 2014-09-23 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
| KR101457858B1 (en) * | 2012-12-14 | 2014-11-04 | 한국타이어 주식회사 | Rubber composition for tire tread and tire manufactured by using the same |
| KR102244900B1 (en) | 2016-07-05 | 2021-04-26 | 주식회사 엘지화학 | Composites having core-shell structure and rubber composition comprising the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211268A (en) * | 1996-12-16 | 1999-03-17 | 株式会社普利司通 | Rubber composition and pneumatic tires produced therefrom |
| CN1541245A (en) * | 2001-08-13 | 2004-10-27 | �����ּ�����˾ | Diena rubber compsn. for tyres comprising specific silicon as reinforcing filler |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100429071B1 (en) | 2001-06-25 | 2004-04-29 | 한국타이어 주식회사 | The rubber composition for tire treads |
| KR100542284B1 (en) * | 2003-09-15 | 2006-01-11 | 금호타이어 주식회사 | Tread Compound for Motorcar |
-
2009
- 2009-12-23 KR KR1020090130218A patent/KR101140248B1/en not_active IP Right Cessation
-
2010
- 2010-11-29 CN CN201010563338XA patent/CN102108142B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1211268A (en) * | 1996-12-16 | 1999-03-17 | 株式会社普利司通 | Rubber composition and pneumatic tires produced therefrom |
| CN1541245A (en) * | 2001-08-13 | 2004-10-27 | �����ּ�����˾ | Diena rubber compsn. for tyres comprising specific silicon as reinforcing filler |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103703072A (en) * | 2011-07-22 | 2014-04-02 | 住友橡胶工业株式会社 | Rubber composition for tread, and pneumatic tire |
| CN103703072B (en) * | 2011-07-22 | 2016-02-03 | 住友橡胶工业株式会社 | Rubber composition for tire tread and pneumatic tyre |
| USRE46184E1 (en) | 2011-07-22 | 2016-10-25 | Sumitomo Rubber Industries, Ltd. | Rubber composition for tread, and pneumatic tire |
| CN102634090A (en) * | 2012-05-02 | 2012-08-15 | 三角轮胎股份有限公司 | Tread rubber composition of fuel-efficient type semi-steel radial tire |
| CN107428202A (en) * | 2015-02-26 | 2017-12-01 | 横滨橡胶株式会社 | Pneumatic belt tire |
| CN107428202B (en) * | 2015-02-26 | 2019-06-21 | 横滨橡胶株式会社 | Pneumatic belt tire |
| CN105670062A (en) * | 2016-01-27 | 2016-06-15 | 北京化工大学 | Wear-resistant tire tread rubber material with high wet skid resistance, low rolling resistance and high performance |
| CN107540900A (en) * | 2016-06-28 | 2018-01-05 | 住友橡胶工业株式会社 | Rubber composition and tire |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102108142B (en) | 2013-05-15 |
| KR101140248B1 (en) | 2012-07-09 |
| KR20110073061A (en) | 2011-06-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102108142B (en) | Rubber composition for tire tread and tire manufactured using composition | |
| CN102101920B (en) | Rubber composition for tire tread and tire manufactured with the same | |
| CN102101926B (en) | Rubber composition for airtight layer of tire and tire manufactured with the same | |
| CN101743273B (en) | Rubber composition for side wall and pneumatic tire utilizing the same | |
| CN101679685B (en) | Ply, clinch and tread formed using specified rubber composition, and pneumatic tire utilizing them | |
| CN110511457B (en) | Rubber composition for tire tread and tire manufactured by using same | |
| KR101614131B1 (en) | Rubber composition for tire tread and tire manufactured by using the same | |
| CN103865132A (en) | Rubber composition for tire tread and tire manufactured by using the same | |
| CN1141311A (en) | Silica reinforced rubber prepn. and tire with tread thereof | |
| CN101755002A (en) | Rubber composition for sidewall and pneumatic tire made with the same | |
| CN101323679A (en) | Rubber composition for carcass ply or band and pneumatic tire using the same | |
| CN105017571A (en) | Sidewall insert rubber composition for run-flat tire and tire produced using the same | |
| CN104419041A (en) | Rubber composition for tire tread and tire manufactured by using the same | |
| CN104592568A (en) | Rubber composition for tire and tire manufactured by using the same | |
| CN104710656A (en) | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same | |
| CN110117388A (en) | Rubber composition for tire tread and the tire manufactured using the composition | |
| CN110343301B (en) | Rubber composition for tire tread, method for producing same, and tire produced using same | |
| CN102149766B (en) | Rubber composition for tire and tire | |
| CN101759889B (en) | Rubber composition for tire tread | |
| CN102372859B (en) | Rubber composition for tire and tire manufactured by using the same | |
| CN103183850B (en) | Rubber composite used for tire face and tire manufactured with the composite | |
| CN105218900A (en) | Rubber composition for tire tread and the tire utilizing said composition to manufacture | |
| CN103172914B (en) | Rubber composition for tyre belt layer and tyre prepared from the composition | |
| CN105367850A (en) | Tire and method for manufacturing tire | |
| CN105273262B (en) | Rubber composition for tire tread and the tire manufactured using said composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130515 Termination date: 20141129 |
|
| EXPY | Termination of patent right or utility model |