CN108794817B - Tire comprising a rubber composition protecting the sidewalls from ozone damage - Google Patents
Tire comprising a rubber composition protecting the sidewalls from ozone damage Download PDFInfo
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- CN108794817B CN108794817B CN201710286433.1A CN201710286433A CN108794817B CN 108794817 B CN108794817 B CN 108794817B CN 201710286433 A CN201710286433 A CN 201710286433A CN 108794817 B CN108794817 B CN 108794817B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- 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
- B60C1/0025—Compositions of the sidewalls
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The present invention relates to a rubber composition capable of protecting a tire sidewall from ozone damage and a tire manufactured using the same. Specifically, the tire comprises an anti-aging rubber sheet between a tire side and a tire body, wherein the anti-aging rubber sheet is manufactured by using a rubber composition comprising 100 parts by weight of raw rubber, 20-60 parts by weight of carbon black and 2-5 parts by weight of an amine anti-aging agent. The tire manufactured by using the rubber composition according to the present invention can remarkably improve the ozone resistance without changing the blackness of the appearance.
Description
Technical Field
The present invention relates to a rubber composition capable of protecting a tire sidewall from ozone damage and a tire manufactured using the same. More particularly, the present invention relates to a rubber composition which has excellent ozone resistance to an aging phenomenon caused by ozone, ultraviolet rays, or the like by disposing a rubber composition in the form of a sheet between a tire sidewall and a carcass, thereby protecting the sidewall from ozone, and a tire manufactured using the same.
Background
The sidewall of a tire is provided with various information related to the tire, and unlike a tread surface in contact with the ground, the sidewall must have characteristics of withstanding external environmental factors such as sunlight, temperature, ozone, and oxygen, and weather influences.
Since the sidewall of the tire is subjected to frequent bending and stretching movements by irradiation of light rays from the sun, and heat generated from the tire needs to be released to the outside, the tire is required to have weather resistance, aging resistance, bending resistance, heat generation resistance, and ozone resistance. To obtain the desired properties of the sidewall, various additives are used. As a material generally used, a rubber composition in which an amine-based antioxidant or a wax is blended in a large amount into a diene-based rubber component has been widely used.
However, such amine-based antioxidants precipitate on the rubber surface with time, thereby discoloring the rubber. In order to prevent such appearance discoloration, an antioxidant is added to the rubber component in a small amount or not at all, and a large amount of wax is blended in place of the antioxidant.
As described above, in the case of a rubber composition using a large amount of wax, the deterioration of appearance due to the amine-based antioxidant can be prevented to some extent while the ozone resistance in a static state is maintained.
However, it has not been possible to solve the problem of deterioration in heat resistance, ozone resistance under dynamic conditions, and weather resistance, which are other physical properties required for the side wall rubber.
In order to solve such problems, amine antioxidants or waxes should not be used, but if amine antioxidants or waxes are not added, the properties mainly required of the sidewall rubber, that is, weather resistance, ozone resistance, and heat resistance, are greatly reduced.
Therefore, efforts are needed to: an optimum mixing ratio of an amine antioxidant is required to minimize discoloration of the tire appearance and to maximize weather resistance, ozone resistance and heat resistance of the tire side, a novel antioxidant is developed to minimize discoloration, or the structure of the tire side is changed.
Prior art documents
Patent document
(patent document 1) Korea publication No. 1995-0003044 (1995.03.30.)
Disclosure of Invention
Technical problem to be solved
The purpose of the present invention is to provide a tire in which a sheet containing a rubber composition for protecting a tire side portion from ozone is positioned between the tire side portion and a carcass.
Means for solving the problems
According to a preferred embodiment of the present invention, there is provided a tire comprising an anti-aging rubber sheet between a sidewall and a carcass, the anti-aging rubber sheet being produced from a rubber composition containing 100 parts by weight of a raw rubber, 20 to 60 parts by weight of carbon black, and 2 to 5 parts by weight of an amine antioxidant.
The amine antioxidant may be any one selected from the group consisting of N-phenyl-N ' - (1, 3-dimethyl) -p-phenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N ' -diaryl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine, N-phenyl-N ' -octyl-p-phenylenediamine, and combinations thereof.
The sidewall may include 100 parts by weight of a raw rubber and 0 part by weight or more and less than 2 parts by weight of an amine antioxidant.
The rubber composition may further include 1 to 3 parts by weight of any one antioxidant selected from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes, and combinations thereof.
The rubber composition may further include 1 to 3 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline.
Effects of the invention
The tire manufactured by using the rubber composition for protecting the tire side wall from the ozone environment according to the present invention does not change the blackness of the appearance, and can also significantly improve the ozone resistance.
Drawings
FIG. 1 is a cross-sectional view of a tire sidewall according to one embodiment of the present invention.
FIG. 2 is an enlarged schematic view of a cross section of a tire side portion according to an embodiment of the present invention.
FIG. 3 is a schematic view of a cross-sectional layer of a tire having a rubber composition disposed between the sidewall and the carcass that protects the sidewall of the tire from ozone according to one embodiment of the present invention.
Description of the reference numerals
1: sidewall
2: tyre body
3: anti-aging rubber sheet
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail to ensure that those skilled in the art can easily carry out the invention. However, the present invention may be embodied in many different forms and is not limited to only the embodiments set forth herein.
The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular forms "a", "an" and "the" include plural referents unless the content clearly dictates otherwise. The terms "comprising" or "having" described in the specification of the present invention should be understood to mean that there are the features, numbers, steps, actions, constituent elements, components, or combinations thereof described in the specification, and the existence or addition possibility of one or more other features or numbers, steps, actions, constituent elements, components, or combinations thereof cannot be previously excluded.
Fig. 1 is a schematic structural view of a cross section of a side portion of a tire, fig. 2 is a schematic view of enlarging the side portion, and fig. 3 is a schematic view of patterning a sheet located between the side portion and a carcass, the sheet containing a rubber composition according to one embodiment of the present invention.
According to an embodiment of the present invention, there is provided a tire including an anti-aging rubber sheet between a sidewall portion and a carcass, the anti-aging rubber sheet may contain a rubber composition to which an amine-based antioxidant is added.
With the aging-resistant rubber sheet, the amine antioxidant migrates to the sidewall portion with the passage of time, and thus the weather resistance, ozone resistance and heat resistance of the sidewall portion can be improved. At the same time, the amount of amine-based aging inhibitor in the sidewall portion is minimized, thereby preventing initial discoloration of the sidewall portion.
The schematic structure of the sidewall portion of the tire is as shown in fig. 1 and 2, and it is composed of the outermost layer, i.e., the sidewall rubber 1, and the carcass 2 supporting the tire structure, between which the anti-aging rubber sheet 3 for protecting the tire sidewall from ozone destruction according to one embodiment of the present invention is disposed.
The rubber sheet 3 for preventing aging according to one embodiment of the present invention may be composed of a rubber composition containing 100 parts by weight of a raw rubber, 20 to 60 parts by weight of carbon black, and 2 to 5 parts by weight of an amine type antioxidant.
The anti-aging rubber sheet 3 may be located between the sidewall rubber 1 and the carcass 2.
In the anti-aging rubber sheet 3 of the present invention, any one or more rubbers selected from the group consisting of natural rubbers, modified natural rubbers, and synthetic rubbers may be used as the raw rubber.
The natural rubber contains cis-1, 4-polyisoprene as a main component, but trans-1, 4-polyisoprene may be contained depending on the required characteristics. Therefore, the natural rubber may contain, for example: natural rubber such as Barlata, which is one of the rubbers of Sapotaceae produced in south America, contains trans-1, 4-isoprene as a main component.
The modified natural rubber is obtained by modifying or purifying the common natural rubber. For example: the modified natural rubber includes Epoxidized Natural Rubber (ENR), deproteinized natural rubber (DPNR), hydrogenated natural rubber, and the like.
The synthetic rubber includes, but is not limited to, a rubber selected from the group consisting of styrene-butadiene rubber (SBR), modified styrene-butadiene rubber, Butadiene Rubber (BR), modified butadiene rubber, isoprene rubber, chloroprene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluororubber, silicone rubber, nitrile rubber, hydrogenated nitrile rubber, Nitrile Butadiene Rubber (NBR), modified nitrile butadiene rubber, chlorinated polyethylene rubber, styrene-ethylene-butylene-styrene (SEBS) rubber, ethylene-propylene-diene monomer (EPDM) rubber, hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, chlorohydrin rubber, vinylbenzyl chloride-styrene butadiene rubber, bromomethylbutyl styrene rubber, maleic acid-styrene butadiene rubber, carboxylic acid styrene-butadiene rubber, epoxy isoprene rubber, maleic acid ethylene propylene rubber, A carboxylic nitrile butadiene rubber, BIMS (brominated polyisobutylisoprene-co-p-methylstyrene), and a mixture thereof.
In particular, the synthetic rubber is preferably butadiene rubber, and more preferably high cis butadiene rubber. The high-cis butadiene rubber may be a product having a cis-1, 4 content of 96 wt% or more and a glass transition temperature (Tg) of-104 to-107 ℃. The high cis-butadiene rubber is more excellent in low temperature characteristics and recovery (recovery) elasticity within the range of cis-1, 4 content and the glass transition temperature.
In order to improve the appearance and prevent tearing and maintain fatigue resistance, the raw rubber may be a mixed rubber composed of a natural rubber or a modified natural rubber mixed with a synthetic rubber. In this case, the natural rubber or modified natural rubber and synthetic rubber may be mixed in a ratio of 1: 9-9: 1 by weight ratio. If the natural rubber or modified natural rubber is contained in an amount less than 1% by weight, fatigue resistance is lowered, resulting in poor appearance. If the synthetic rubber is contained in an amount less than 1% by weight, the tear resistance and the fracture resistance are deteriorated.
In the anti-aging rubber sheet 3 of the present invention, the amine antioxidant may be used in a proportion of 2 to 5 parts by weight per 100 parts by weight of the raw material rubber, the amine antioxidant is any one selected from the group consisting of N-phenyl-N ' - (1, 3-dimethyl) -p-phenylenediamine (6PPD), N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine (IPPD), N ' -diphenyl-p-phenylenediamine, N ' -diaryl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine, N-phenyl-N ' -octyl-p-phenylenediamine, and combinations thereof. More preferably, 6PPD or IPPD, which is excellent in both heat aging resistance and ozone resistance, may be used as the amine-based antioxidant. If the amine-based antioxidant is used in an amount of less than 2 parts by weight, the antioxidant effect is insufficient. If it exceeds 5 parts by weight, the migration (migration) thereof to the sidewall portion is increased, resulting in discoloration.
The type of carbon black contained in the anti-aging rubber sheet 3 of the present invention is not particularly limited, but preferably, the BET (Brunauer, Emmett, Teller) specific surface area is 70 to 100m2The DBP (dibutyl n-phthalate) adsorption value is 100-110 g/100g, and the iodine adsorption value is in the range of 90-120 mg/g. When the nitrogen adsorption specific surface area, the DBP oil absorption and the iodine adsorption value of the carbon black are in the above ranges, a rubber composition for a tire having both suitable reinforcing properties and suitable processability can be produced.
Representative examples of such carbon blacks include, but are not limited to, N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N539, N550, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990, or N991, and the like.
The carbon black may be used in an amount of 20 to 60 parts by weight per 100 parts by weight of the raw rubber. If the carbon black is used in an amount of less than 20 parts by weight, the rubber sheet will have insufficient reinforcing properties, resulting in a reduction in tire durability. If the carbon black is used in an amount exceeding 60 parts by weight, the hysteresis of the rubber sheet is increased, thereby reducing the fuel economy performance of the tire.
In addition, the rubber sheet 3 for aging prevention of the present invention may further contain an additional antioxidant in addition to the amine antioxidant. The anti-aging agent is an additive used for stopping the chain reaction of auto-oxidation of the tire under the action of oxygen. The antioxidant may be used by appropriately selecting any one from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes, and combinations thereof.
The phenol-based antioxidant may be any one selected from the group consisting of phenol-based 2,2 '-methylene-bis (4-methyl-6-tert-butylphenol), 2' -isobutylene-bis (4, 6-xylenol), 2, 6-di-tert-butyl-p-cresol, and combinations thereof.
The quinoline antioxidant may be 2,2, 4-trimethyl-1, 2-dihydroquinoline or a derivative thereof, and specifically, may be any one selected from the group consisting of 6-ethoxy-2, 2, 4-trimethyl-1, 2-dihydroquinoline, 6-anilino-2, 2, 4-trimethyl-1, 2-dihydroquinoline, 6-dodecyl-2, 2, 4-trimethyl-1, 2-dihydroquinoline, and a combination thereof.
The wax is preferably a waxy hydrocarbon.
The antioxidant other than amines is required to have an anti-aging effect, and must have the following conditions: the solubility to rubber is high; low volatility and must be inert to rubber; sulfur addition cannot be inhibited, etc. In consideration of the above conditions, the antioxidant is contained in an amount of 1 to 3 parts by weight per 100 parts by weight of the raw rubber.
More preferably, the anti-aging rubber sheet 3 of the present invention further contains 1 to 3 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline (RD) per 100 parts by weight of the raw material rubber. RD is inferior to 6PPD or IPPD in ozone resistance, but is inexpensive and superior in physical properties such as thermal aging resistance and fatigue resistance. The higher the content of RD, the more the amine antioxidant migrates to the sidewall rubber, whereby the ozone resistance can be improved.
If the amount of RD is less than 1 part by weight, the movement of the amine-based antioxidant in the rubber sheet for anti-aging is restricted, and the anti-aging effect cannot be exerted on the sidewall portion. If it exceeds 5 parts by weight, the migration of the amine-based antioxidant is excessively promoted, thereby causing discoloration of the sidewall portion caused by the amine-based antioxidant. In addition, excessive use of RD reduces the adhesion between the anti-aging rubber sheet and the sidewall rubber or carcass rubber, resulting in a decrease in tire durability.
The rubber sheet 3 for anti-aging containing the amine antioxidant can be used in a predetermined amount according to the compounding ratio used in a general tire rubber composition, by selecting various additives commonly used in the art to which the present invention pertains, such as a reinforcing agent, an activator, a processing oil, a vulcanizing agent, and a vulcanization accelerator, as needed.
The vulcanizing agent is preferably a sulfur-based vulcanizing agent. The sulfur vulcanizing agent may be inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur, precipitated sulfur, colloidal sulfur, elemental sulfur, and polymer sulfur, and a vulcanizing agent for producing sulfur, such as: organic sulfides such as amine disulfide (TMTD), tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), and dithiodimorpholine (dithiodimorphine).
If the vulcanizing agent is 1.5-2.5 parts by weight relative to 100 parts by weight of the raw material rubber, a proper vulcanizing effect can be obtained, so that the raw material rubber is not sensitive to heat and can keep good chemical stability.
The vulcanization accelerator is an accelerator (initiator) for accelerating the vulcanization rate or accelerating the retarding action at the initial vulcanization stage.
The vulcanization accelerator may be any one selected from the group consisting of sulfenamides, thiazoles, thiurams, thioureas, guanidines, dithiocarbamates, aldamines, aldimines, imidazolines, xanthates, and combinations thereof.
The sulfenamide-based vulcanization accelerator may be any sulfenamide-based compound selected from the group consisting of, for example, N-cyclohexyl-2-benzenesulfenamide (CBS), N-tert-butyl-2-benzenesulfenamide (TBBS), N-dicyclohexyl-2-benzenesulfenamide, N-oxydiethyl-2-benzenesulfenamide, N-diisopropyl-2-benzothiazolesulfenamide, and combinations thereof.
The thiazole vulcanization accelerator may be any thiazole compound selected from the group consisting of 2-Mercaptobenzothiazole (MBT), dibenzothiazole disulfide (MBTS), 2-mercaptobenzothiazole sodium salt, 2-mercaptobenzothiazole zinc salt, 2-mercaptobenzothiazole copper salt, 2-mercaptobenzothiazole cyclohexylamine salt, 2- (2, 4-dinitrophenyl) mercaptobenzothiazole, 2- (2, 6-diethyl-4-morpholinothio) benzothiazole and combinations thereof.
The thiuram based vulcanization accelerator may be any one selected from the group consisting of tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylenethiuram disulfide, dipentamethylenethiuram monosulfide, dipentamethylenethiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, cyclopentanthiuram tetrasulfide, and combinations thereof.
The thiourea-based vulcanization accelerator may be any one thiourea-based compound selected from the group consisting of thiourea, diethylthiourea, dibutylthiourea, trimethylthiourea, di-o-tolylthiourea, and combinations thereof.
The guanidine vulcanization accelerator may be any guanidine compound selected from the group consisting of diphenylguanidine, di-o-tolylguanidine, triphenylguanidine, o-tolylbiguanide, diphenylguanidine phthalate, and combinations thereof.
The vulcanization accelerator of dithiocarbamic acid may be selected from the group consisting of zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate, zinc dipentyldithiocarbamate, zinc dipropyldithiocarbamate, zinc pentamethylenedithiocarbamate and piperidine complex salt, any one of dithiocarbamic acid compounds selected from the group consisting of zinc cetylisopropyl dithiocarbamate, zinc octadecylisopropyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, cadmium diamyldithiocarbamate, and combinations thereof is used.
The aldehyde amine or aldehyde ammonia vulcanization accelerator may be any one of aldehyde amine or aldehyde ammonia compounds selected from the group consisting of an acetaldehyde-aniline reactant, a butylaldehyde-aniline condensate, hexamethylenetetramine, an acetaldehyde-ammonia reactant, and a combination thereof.
As the imidazoline based vulcanization accelerator, an imidazoline based compound such as 2-mercaptoimidazoline can be used, and as the xanthate based vulcanization accelerator, a xanthate based compound such as zinc dibutylxanthate can be used.
The vulcanization accelerator is contained in an amount of 0.6 to 1.2 parts by weight per 100 parts by weight of the raw rubber in order to maximize the productivity by accelerating the vulcanization rate and enhance the physical properties of the rubber.
The vulcanization accelerator may be used as a compounding agent used together with the vulcanization accelerator to sufficiently exhibit the accelerating effect thereof, and may be selected from the group consisting of inorganic vulcanization accelerators, organic vulcanization accelerators, and combinations thereof.
The inorganic vulcanization accelerator may be any one selected from the group consisting of Zinc Oxide (ZnO), Zinc Carbonate (Zinc Carbonate), magnesium Oxide (MgO), Lead Oxide (Lead Oxide), potassium hydroxide, and combinations thereof. The organic vulcanization accelerator may be used in any one selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate (dibutyl ammonium oleate), derivatives thereof, and combinations thereof.
In particular, the vulcanization-accelerating assistant may use the zinc oxide together with the stearic acid. In this case, the zinc oxide dissolves in the stearic acid and forms an effective complex (complex) with the vulcanization accelerator, so that free sulfur is generated in the vulcanization reaction, and the crosslinking reaction of the rubber becomes easier.
When the zinc oxide is used together with the stearic acid, in order to function as a suitable vulcanization-accelerating assistant, 2.0 to 4.0 parts by weight of each of the zinc oxide and the stearic acid is used per 100 parts by weight of the raw rubber. If the contents of the zinc oxide and the stearic acid are less than the above ranges, the vulcanization rate is lowered, resulting in a decrease in production efficiency. If the amount exceeds the above range, scorching occurs and the physical properties are deteriorated.
The softener is added to the rubber composition in order to impart plasticity to the rubber to make the processing easier or to reduce the hardness of the vulcanized rubber, and it means other materials such as oils used in compounding the rubber or in producing the rubber. The softener refers to oils contained in process oil (process oil) or other rubber compositions. The softener may be any one selected from the group consisting of petroleum oils, vegetable fats and oils, and combinations thereof, but the present invention is not limited thereto.
The petroleum oil may be any one selected from the group consisting of paraffinic oil, naphthenic oil, aromatic oil, and combinations thereof.
Representative examples of the paraffinic oils include P-1, P-2, P-3, P-4, P-5, P-6, etc., produced by Mechang oil Co., Ltd, representative examples of the naphthenic oils include N-1, N-2, N-3, etc., produced by Mechang oil Co., Ltd, and representative examples of the aromatic oils include A-2, A-3, etc., produced by Mechang oil Co., Ltd.
However, with the increasing awareness of environmental protection, it has been recognized that when the Aromatic oils contain Polycyclic Aromatic Hydrocarbons (hereinafter referred to as "PAHs") in an amount exceeding 3% by weight, the possibility of inducing cancer is high. Therefore, TDAE (treated distilled aromatic extract) oil, MES (Mild extraction solvent) oil, RAE (residual aromatic extract) oil or heavy naphthenic oil may be preferably used.
In particular, the oil used as the softener is preferably a TDAE oil having a kinematic viscosity of 95 DEG F or more (210 DEG F SUS) and containing 15 to 25 wt% of an aromatic component, 27 to 37 wt% of a naphthenic component and 38 to 58 wt% of a paraffinic component, based on the total content of PAHs components in the whole oil.
TDAE oil not only can make contain the tire side wall of TDAE oil has good low temperature characteristic, oil consumption performance, but also is favorable to environmental protection, reduces the carcinogenic risk of PAHs.
The vegetable oil may be any one selected from the group consisting of castor oil, cotton seed oil, linseed oil, canola oil, soybean oil, palm oil, coconut oil, peanut oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower seed oil, palm kernel oil, camellia oil, jojoba oil, macadamia nut oil, safflower seed oil, tung oil, and combinations thereof.
The softener is 2.0-6.0 parts by weight relative to 100 parts by weight of the raw material rubber, so that the processability of the raw material rubber is improved.
The sidewall rubber composition 1 of the present invention does not use an amine-based antioxidant or is used in an amount less than 1 part by weight, and therefore can prevent discoloration of the sidewall portion. Meanwhile, the anti-aging rubber sheet 3 containing 2 to 5 parts by weight of the amine antioxidant can prevent ozone cracking and cracking caused by aging which may occur during use.
The anti-aging rubber sheet 3 and the sidewall rubber composition 1 can be produced by a conventional 2-step continuous production process. I.e. can be produced in a suitable mixer by the following two steps: that is, the step 1 of performing thermomechanical treatment or kneading under a condition of a maximum temperature of 110 to 190 ℃, preferably, a high temperature of 130 to 180 ℃ (referred to as "non-production step"); during the final (finishing) step of the mixing of the cross-linked binding system, at temperatures typically below 110 ℃, for example: the 2 nd step of mechanical treatment (referred to as "production step") is carried out at a low temperature of 40 to 100 ℃, but the present invention is not limited thereto.
The anti-aging rubber sheet and the sidewall rubber composition are not limited to the sidewall portion, and may be included in various rubber components constituting the tire. The rubber components comprise a tire tread, an apex (apex), a chafer, a wire coating (wire coat) or an airtight layer and the like.
According to another embodiment of the invention, the anti-aging rubber sheet 3 is arranged between the sidewall 1 and the tire body 2 in a sheet shape. The method for manufacturing a tire comprising the anti-aging rubber sheet may employ any method for manufacturing a tire according to the prior art, and a detailed description thereof will be omitted in this specification.
Tires according to another embodiment of the present invention include passenger car tires, racing tires, airplane tires, agricultural tires, off-the-road tires, truck tires, or bus tires, among others. In addition, the tire may be a radial or bias tire, preferably a radial tire.
Hereinafter, preferred examples are given to help understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the present invention is not limited thereto.
[ production example: production of rubber composition
Rubber compositions of production examples 1 to 3 were produced using the compositions shown in table 1 below. The rubber composition of production example 1 was a rubber composition for a sidewall, and the rubber compositions of production examples 2 and 3 were rubber compositions for protecting a sidewall from ozone. The rubber composition can be produced by a method for producing a general rubber composition, and is not particularly limited.
[ TABLE 1]
| Production example 1 | Production example 2 | Production example 3 | |
| Natural rubber1) | 50 | 50 | 50 |
| Butadiene rubber2) | 50 | 50 | 50 |
| Carbon black3) | 50 | 50 | 50 |
| 6PPD4) | - | 3 | 3 |
| |
1 | 1 | 2 |
| |
1 | 1 | 1 |
| Processing oil7) | 5 | 5 | 5 |
| |
3 | 3 | 3 |
| |
1 | 1 | 1 |
| Sulfur | 1.8 | 1.8 | 1.8 |
| Vulcanization accelerator8) | 0.7 | 0.7 | 0.7 |
(unit: parts by weight)
1) Natural rubber: TSR20 rating
2) Butadiene Rubber (BR): butadiene rubber having a Tg (glass transition temperature) of-106 ℃ (BR 1208 made by LG Chemicals)
3) Carbon black: n330
4)6 PPD: N-phenyl-N' - (1, 3-dimethyl) -p-phenylenediamine (Kumanox-13, a product of Jinhu petrochemical)
5) RD: 2,2, 4-trimethyl-1, 2-dihydroquinoline (Vulkanox HS/LG, Langshan)
6) WAX: paraffin wax
7) Processing oil: softener for TDAE (treated distilled aromatic extract) oil
8) Vulcanization accelerator (b): TBBS (N-tert-butyl-2-benzenesulfenamide)
[ comparative example ]
For the manufacture of the tire, the sidewall portion was manufactured using the rubber composition manufactured in the above-described manufacturing example 1, and the carcass portion was manufactured using a generally used rubber composition for a carcass.
[ example 1]
The rubber composition for protecting the tire sidewall from ozone damage manufactured in the manufacturing example 2 was added in a sheet form between the sidewall portion and the carcass portion containing the rubber composition manufactured in the manufacturing example 1, thereby manufacturing a tire.
[ example 2]
The rubber composition for protecting the tire sidewall from ozone damage produced in the production example 3 was added in a sheet form between the sidewall portion and the carcass portion containing the rubber composition produced in the production example 1, thereby producing a tire.
Experimental example evaluation of ozone resistance of tire side portion
Only the tire side portions of the comparative examples and examples were cut, aged in an environment having an ozone concentration of 50pphm and a temperature of 40 ℃, and then the degree of ozone fracture generation was observed, and the results were numerically treated and compared as shown in table 2.
[ TABLE 2]
| Comparative example | Example 1 | Example 2 | ||
| Static ozone resistance | C4 | B1 | A1 | |
| Appearance of the | Level | 1 | |
|
Number of cracks: a < B < C
Size of crack: 1<2<3<4<5
Evaluation of blackness: class 1-blackness hardly changed.
Grade 2-a slight decrease in blackness.
Grade 3-the degree of blackness varies significantly.
As shown in the results in table 2, in examples 1 and 2 in which the rubber sheet for anti-aging containing an amine-based anti-aging agent was used, the ozone resistance was significantly improved as compared with the comparative example in which only the sidewall rubber composition was used without using the sheet. The degree of discoloration caused by the amine-based aging resistor maintained the standard similar to that of the comparative example not containing the amine-based aging resistor.
Further, as can be seen from example 2, if the content of RD in the anti-aging rubber sheet is increased, the migration of the amine-based antioxidant to the side wall rubber is increased, and the static ozone resistance can be improved.
Based on the above results, by disposing the rubber sheet for anti-aging between the sidewall portion and the carcass portion, the content of the amine-based anti-aging agent causing discoloration in the sidewall portion rubber composition can be reduced to less than 2 parts by weight, more preferably, to 1 part by weight or less.
In the foregoing specification, preferred embodiments of the present invention have been described in detail. However, the scope of the present invention is not limited thereto, and various modifications and improvements that can be made by those skilled in the art using the basic concept of the present invention defined in the claims also belong to the scope of the present invention.
Claims (4)
1. A tire, characterized by:
comprising an anti-aging rubber sheet disposed between a sidewall and a carcass,
the rubber sheet for anti-aging comprises a rubber composition containing: 100 parts of raw material rubber, 20-60 parts of carbon black and 2-5 parts of amine anti-aging agent,
the sidewall comprises: 100 parts of raw material rubber and more than 0 part and less than 2 parts of amine anti-aging agent.
2. The tire of claim 1, wherein:
the amine antioxidant is any one selected from the group consisting of N-phenyl-N ' - (1, 3-dimethyl) -p-phenylenediamine, N- (1, 3-dimethylbutyl) -N ' -phenyl-p-phenylenediamine, N-phenyl-N ' -isopropyl-p-phenylenediamine, N ' -diphenyl-p-phenylenediamine, N ' -diaryl-p-phenylenediamine, N-phenyl-N ' -cyclohexyl-p-phenylenediamine, N-phenyl-N ' -octyl-p-phenylenediamine, and combinations thereof.
3. The tire of claim 1, wherein:
the rubber composition further comprises 1-3 parts by weight of any one antioxidant selected from the group consisting of phenols, quinolines, imidazoles, metal carbamates, waxes, and combinations thereof.
4. The tire of claim 1, wherein:
the rubber composition further comprises 1-3 parts by weight of 2,2, 4-trimethyl-1, 2-dihydroquinoline.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710286433.1A CN108794817B (en) | 2017-04-27 | 2017-04-27 | Tire comprising a rubber composition protecting the sidewalls from ozone damage |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710286433.1A CN108794817B (en) | 2017-04-27 | 2017-04-27 | Tire comprising a rubber composition protecting the sidewalls from ozone damage |
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| CN108794817A CN108794817A (en) | 2018-11-13 |
| CN108794817B true CN108794817B (en) | 2020-12-18 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118695A1 (en) * | 2004-05-26 | 2005-12-15 | Pirelli Tyre S.P.A. | Tire comprising an elastomeric polymer including a functional group and crosslinkable elastomeric composition |
| CN1923933A (en) * | 2005-09-02 | 2007-03-07 | 李宝杰 | Ageing-proof coating for rubber |
| CN1944507A (en) * | 2005-10-05 | 2007-04-11 | 韩国轮胎株式会社 | Insert for run-flat tyre and rubber composition of tyre bead filling |
| CN101117409A (en) * | 2007-07-14 | 2008-02-06 | 昊华南方(桂林)橡胶有限责任公司 | All-steel giant-scale engineering tyre side glue and all-steel giant-scale engineering tyre using the same |
| CN103642092A (en) * | 2013-11-26 | 2014-03-19 | 山东永泰化工有限公司 | Ozone and aging resistant sidewall rubber for heavy trucks |
| CN104710656A (en) * | 2013-12-17 | 2015-06-17 | 韩国轮胎株式会社 | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same |
| CN105602035A (en) * | 2016-03-02 | 2016-05-25 | 山东玲珑轮胎股份有限公司 | Tread rubber material for sidewall and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8299161B2 (en) * | 2005-12-28 | 2012-10-30 | Bridgestone Corporation | Defatted soy flour/natural rubber blends and use of the blends in rubber compositions |
-
2017
- 2017-04-27 CN CN201710286433.1A patent/CN108794817B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005118695A1 (en) * | 2004-05-26 | 2005-12-15 | Pirelli Tyre S.P.A. | Tire comprising an elastomeric polymer including a functional group and crosslinkable elastomeric composition |
| CN1923933A (en) * | 2005-09-02 | 2007-03-07 | 李宝杰 | Ageing-proof coating for rubber |
| CN1944507A (en) * | 2005-10-05 | 2007-04-11 | 韩国轮胎株式会社 | Insert for run-flat tyre and rubber composition of tyre bead filling |
| CN101117409A (en) * | 2007-07-14 | 2008-02-06 | 昊华南方(桂林)橡胶有限责任公司 | All-steel giant-scale engineering tyre side glue and all-steel giant-scale engineering tyre using the same |
| CN103642092A (en) * | 2013-11-26 | 2014-03-19 | 山东永泰化工有限公司 | Ozone and aging resistant sidewall rubber for heavy trucks |
| CN104710656A (en) * | 2013-12-17 | 2015-06-17 | 韩国轮胎株式会社 | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same |
| CN105602035A (en) * | 2016-03-02 | 2016-05-25 | 山东玲珑轮胎股份有限公司 | Tread rubber material for sidewall and application |
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|---|---|
| CN108794817A (en) | 2018-11-13 |
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