KR101647328B1 - Curing bladder for tire and tire manufactured by using the same - Google Patents

Abstract

In the present invention, a vulcanizing bladder for a tire vulcanizing agent capable of improving the vulcanization degree of a finished tire by supplying a uniform heat source to each gauge of the tire and increasing the rubber strength to increase the durability and the rotation resistance of the tire, A tire is provided.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a vulcanizing bladder for a vulcanizing tire,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bladder for vulcanizing a tire and a tire manufactured using the bladder.

In general tire manufacturing, a green tire completed in a tire molding process is put into a vulcanizing mold, and then vulcanized for a predetermined time under heat and pressure applied to the inside / outside of the green tire, so that the rubber vulcanizing agent and rubber A vulcanization operation is carried out to crosslink the molecules to obtain stable inherent properties of the tire rubber.

A vulcanizing bladder is installed inside the green tire to apply heat and pressure to the inside of the tire in the green tire vulcanizing operation and the vulcanized bladder is expanded by supplying steam and inert nitrogen gas into the vulcanizing bladder, Is brought into close contact with the mold. Accordingly, the bladder is an important component that greatly affects the tire manufacturing and appearance quality.

1, the thickness of the green tire 1 ranges from the tread portion 1a to the shoulder portions 1b and 1b ', the side wall portions 1b and 1c' and the bead portions 1d and 1d ' It changes continuously. Therefore, when the internal heat source is transferred to the green tire 1 with the bladder 2 having a constant thickness, it is difficult to transmit uniform heat amount due to the thickness change of the green tire. As a result, the thickness of the green tire (or the gauge) of the tread 1a is unfavorably increased, and the thinner portion such as the sidewalls 1c and 1c ' So that the bladder 2 having a constant thickness can cause the vulcanization of the finished tire to deteriorate.

Korean Registered Patent No. 1140184 (Registered on Apr. 19, 2012)

SUMMARY OF THE INVENTION It is an object of the present invention to provide a tire vulcanizing bladder which can improve the durability and the rotation resistance of a tire by solving the above problems, improving the vulcanization degree of the tire, and increasing the strength of vulcanized rubber.

Another object of the present invention is to provide a tire manufactured using the tire vulcanizing bladder.

In order to achieve the above object, a tire vulcanizing bladder according to an embodiment of the present invention includes a tread which is a rubber layer in contact with a road surface, a tire including a shoulder portion, a sidewall and a bead portion sequentially extending from both sides of the tread, A first bladder portion including a tread corresponding portion and a shoulder portion corresponding to the tread and the shoulder in the first bladder portion; And a second bladder portion including a side wall corresponding portion and a bead portion corresponding portion corresponding to the side wall and the bead portion of the tire, wherein the first bladder portion includes at least one of natural rubber and butyl rubber Wherein the rubber blend is produced using a rubber composition for forming a first bladder portion comprising 10 to 20 parts by weight of carbon black and 1 to 5 parts by weight of graphene based on 100 parts by weight of the raw rubber, Thickness.

Wherein the first bladder portion has a thickness of 2 to 5 mm and the second bladder portion has a thickness of 5 to 20 m but the first bladder portion has a thickness of the second bladder portion It may be thinner.

In the tire vulcanizing bladder, the thickness tends to increase toward the shoulder portion corresponding portion, the tread corresponding portion, the bead portion corresponding portion, and the sidewall corresponding portion.

The tread corresponding portion may have a thickness of 3 to 5 mm, the shoulder portion corresponding portion may have a thickness of 2 to 3 mm, the sidewall corresponding portion may have a thickness of 10 to 20 mm, and the bead portion may have a thickness of 5 to 10 mm.

In the first bladder, the raw rubber may include 70 to 90 parts by weight of natural rubber and 10 to 30 parts by weight of butyl rubber.

The graphene may have a surface area of 100 to 3,000 m ² / g.

The carbon black may have an iodine (I ₂ ) adsorption value of 50 to 300 mg / g and an adsorption amount of dibutyl phthalate of 80 to 200 ml / 100 g.

The rubber composition for forming a first bladder may further comprise 0.5 to 5 parts by weight of a vulcanizing agent, 0.1 to 3 parts by weight of a vulcanization accelerator, and 0.1 to 10 parts by weight of an antioxidant based on 100 parts by weight of the raw rubber.

A tire according to another embodiment of the present invention is manufactured using the bladder for vulcanizing a tire.

Hereinafter, the present invention will be described in more detail.

Unless otherwise specified herein, the term " tire " includes not only the final manufactured tire but also the green tire before vulcanization.

In the present invention, the bladder is formed by two different rubber compositions, and the thickness (or gauge) of the bladder is varied depending on the position, thereby improving the vulcanization degree of the tire and increasing the strength of the vulcanized rubber, Thereby improving the durability and the rotation resistance.

That is, the bladder for vulcanizing tire according to an embodiment of the present invention includes a tread which is a rubber layer in contact with a road surface, a tire including a shoulder portion, a sidewall and a bead portion sequentially extending from both sides of the tread, A first bladder portion including a tread corresponding portion and a shoulder portion corresponding portion corresponding to the tread and the shoulder portion and a second bladder portion corresponding to the side wall corresponding portion and the bead portion corresponding to the side wall and the bead portion in the tire, Wherein the first bladder portion comprises 10 to 20 parts by weight of carbon black and 1 to 5 parts by weight of graphene based on 100 parts by weight of the raw rubber containing at least one of natural rubber and butyl rubber And has a thickness smaller than the thickness of the second bladder portion.

2 is a cross-sectional view schematically showing a green tire having a bladder for vulcanizing tire according to an embodiment of the present invention installed inside. FIG. 2 is an illustration for illustrating the present invention, but the present invention is not limited thereto.

2, the tire vulcanization bladder 200 according to the present invention includes a tread which is a thick rubber layer in contact with a road surface, and a shoulder portion, a sidewall and a bead portion sequentially extending from both sides of the tread A first bladder portion 10 corresponding to a region including a tread and a shoulder portion of the green tire 100 and a second bladder portion 20 corresponding to a region including the side wall and the bead portion .

The first bladder portion 10 and the second bladder portion 20 may have different thicknesses and the thickness variations in the first bladder portion 10 and the second bladder portion 20 may be different from each other, And the thickness of the rubber in the rubber layer.

Specifically, the first bladder portion 10 corresponding to the tread and the shoulder portion of the tire of relatively thick rubber thickness is thinner than the second bladder portion 20 corresponding to the side wall and bead portion having a relatively small rubber thickness May be desirable. As described above, the first bladder portion 10 is thinner than the second bladder portion 20, so that it is possible to prevent the occurrence of overflow in the sidewall during the vulcanization process of the green tire.

More specifically, it is preferable that the first bladder portion 10 has a thickness of 2 to 5 mm and the second bladder portion 20 has a thickness of 5 to 20 m.

The first bladder portion 10 is divided into a tread corresponding portion 10a corresponding to the tread of the tire and a shoulder portion corresponding portion 10b, 10b 'corresponding to the shoulder portion, and the second bladder portion 20 corresponding to the side walls of the tire are divided into the side wall corresponding portions 20a, 20a 'corresponding to the side walls of the tire and the bead portion corresponding portions 20b, 20b' corresponding to the bead portions, the tread corresponding portion 10a, The side wall corresponding portions 20a and 20a 'and the bead portion corresponding portions 20b and 20b' are formed in the shoulder portion corresponding portions 10b and 10 ', the tread corresponding portion 10a, It may be preferable to have a thickness increasing toward the bead portion corresponding portions 20b and 20b 'and the side wall corresponding portions 20a and 20a'. More specifically, the tread corresponding portion 10a is 3 to 5 mm, the shoulder portion corresponding portions 10b and 10b 'are 2 to 3 mm, the side wall corresponding portions 20a and 20a' are 10 to 20 mm, It is preferable that the bead portion corresponding portions 20b and 20b 'have 5 to 10 mm.

As the thickness (or the gauge) of the green tire 100 increases, the thickness of the bladder 200 corresponding to the green tire 100 decreases, and the thickness of the bladder 200 corresponding to the green tire 100 decreases. Or the quality of the vulcanization can be improved without fear of occurrence of uncrosslinked matters.

In the bladder 200, the first bladder portion 10 and the second bladder portion 20 have different rubber compositions. Specifically, the first bladder portion 10 may include a graphene having excellent thermal conductivity so as to exhibit a higher thermal conductivity than the second bladder portion 20.

More specifically, the first bladder part 10 is formed by blending 10 to 20 parts by weight of carbon black and 1 to 5 parts by weight of graphene with respect to 100 parts by weight of raw rubber containing at least one of natural rubber and butyl rubber The rubber composition for forming a first bladder portion can be produced according to a conventional bladder manufacturing method.

In the rubber composition for forming the first bladder part, the graphene has a structure in which carbon atoms arranged in a hexagonal net shape are continuously bonded, excellent physical and chemical stability, and excellent thermal conductivity and strength characteristics.

The graphene is generally produced by a mechanical exfoliation method using a scotch-tape, a graphite oxidation ultrasonic disruption method, a chemical vapor deposition method, an epitaxy synthesis method, an organic synthesis method using tetraphenylbenzene, or the like However, the production method thereof is not particularly limited in the present invention.

The graphene may have a surface area of 100 to 3,000 m ² / g. By having such a large surface area, the improvement effect in terms of thermal, mechanical, and physical properties is even greater when the same amount is used.

The graphene may be surface-modified to increase the dispersibility of the graphene in the rubber composition. Specifically, the graphene may be prepared by using an organic compound containing a carboxyl group such as aminobenzoic acid, The carboxyl group may be surface-modified to form a covalent bond with the graphene surface. In the surface-modified graphene, the weight ratio of the graphene and the organic compound containing a carboxyl group may be preferably 10:90 to 90:10. When the content of the carboxyl group-containing organic compound is less than 10, the effect of improving the graphene dispersibility is insignificant. When the content of the organic compound exceeds 90, the degree of improvement of the effect is smaller than that of using an excessive amount of organic compound. The effect may be negligible.

The graphene may be contained in an amount of 1 to 5 parts by weight based on 100 parts by weight of the raw rubber. When the content of the graphene is less than 1 part by weight, the strength strengthening effect is insignificant. When the content of the graphene is more than 5 parts by weight, the thermal conductivity may be excessively increased.

On the other hand, in the rubber composition for forming the first bladder part, the raw rubber includes at least one of natural rubber and butyl rubber.

The natural rubber may be a general natural rubber or a modified natural rubber.

The above-mentioned general natural rubber may be used as long as it is known as natural rubber, and the country of origin and the like are not limited. The natural rubber includes cis-1,4-polyisoprene as a main component, but may also include trans-1,4-polyisoprene depending on required characteristics. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main component, natural rubber including trans-1,4-isoprene as a main component, such as balata, Rubber may also be included.

The modified natural rubber may be one obtained by modifying or refining the general natural rubber. Examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.

Among them, an epoxidized natural rubber having excellent air permeability and high thermal conductivity and capable of improving tire productivity may be more preferable. In addition, since the epoxidized natural rubber is biodegradable, it is possible to produce an environment-friendly vulcanizing bladder.

The butyl rubber is a high molecular substance in which a large amount of isobutylene units and a small amount of isoprene are irregularly distributed in the molecule, and is usually an isobutylene-isoprene copolymer rubber having a degree of saturation of 0.5 to 2.5 mol%. The butyl rubber is amorphous under normal conditions, but when stretched it crystallizes like a fiber. Since isoprene in the rubber has a 1,4-bond structure in general, it is produced as a linear polymer and unlike natural rubber, it crystallizes even when cooled And does not lose elasticity even at -50 ° C.

In addition, the butyl rubber is excellent in chemical resistance, has a low gas permeability, is not sensitive to aging by oxygen, but is softened rather than being crumbled by oxidation, rather than other elastomers except silicone. It is more resistant to ozone than natural rubber, has high acid resistance, good solvent resistance, and is excellent in mechanical and electrical properties, and is widely used for tire tubes, tube-less tires, and other mechanical products.

In addition, the butyl rubber has an excellent thermal conductivity and enhances the vulcanization properties by increasing the thermal conductivity in the vulcanization process for the green tire.

More preferably, the raw rubber containing at least one of the natural rubber and the butyl rubber may further include 70 to 90 parts by weight of natural rubber and 10 to 30 parts by weight of butyl rubber. When the natural rubber and the butyl rubber are contained at the mixing ratio as described above, the tire vulcanizing bladder manufactured by using the rubber vulcanizing blender is used in the vulcanization process of a large number of green tires and can exhibit excellent lifespan characteristics even if repeated expansion and contraction are repeated.

In the rubber composition for forming the first bladder part, the carbon black serves as a reinforcing filler.

Silica used as a reinforcing agent in a rubber composition for a tire generally has excellent reinforcing performance, but there is a fear that the abrasion resistance of the rubber composition is lowered. On the other hand, carbon black has no fear of degradation of abrasion resistance and is superior to silica in terms of reinforcing performance. In the present invention, the iodine (I ₂ ) adsorption amount is 50 to 300 mg / g and the n-dibutyl phthalate (DBP) adsorption amount is 80 to 200 ml / g in the carbon black having excellent abrasion resistance and reinforcing performance, 100 g of carbon black is used to maximize the reinforcing property of the vulcanized bladder rubber to enhance the heat resistance and the heat aging resistance of the rubber bladder rubber. black shall meet the above-described I ₂ adsorption value and a DBP adsorption amount condition at the same time. If, even when the carbon black to be used satisfy the conditions of the aforementioned I ₂ adsorption value reinforced by the case where the amount of DBP absorption 80ml / 100g below the filler is carbon black If the DBP adsorption amount exceeds 200 ml / 100 g, the workability and the elongation percentage may be lowered. On the other hand, when the I ₂ adsorption value is less than 50 mg / g There is a possibility that the reinforcing property and the abrasion resistance are lowered, and when it is more than 300 mg / g, there is a possibility that the elongation percentage is lowered.

Further, it is preferable that the adsorbed amount of iodine (I2) is 190 to 205 mg / g, the DBP oil absorption amount is 128 to 140 ml / 100 g, the STSA specific surface area is 151 to 163 m 2 / g and the cDBP oil absorption amount Carbon black having an ultrahigh surface area of 88 to 105 ml / 100 g and a TINT value of 135 to 150 may be more preferable because it can improve the stretchability and heat aging resistance of the bladder and improve the lifespan characteristics remarkably.

The carbon black may be selected from the group consisting of N110, N121, N134, N220, N231, N234, N242, N293, N299, S315, N326, N330, N332, N339, N343, N347, N351, N358, N375, N582, N630, N642, N650, N683, N754, N762, N765, N774, N787, N907, N908, N990 or N991.

In addition to the above-mentioned components, the rubber composition for forming the first bladder portion may optionally improve the physical properties of the rubber composition for forming a tire vulcanizing bladder such as vulcanizing agent, vulcanization accelerator, vulcanization accelerator, softening agent, May further include one or more additives.

Specifically, the vulcanizing agent may be a sulfur vulcanizing agent, an organic peroxide, a resin vulcanizing agent, a metal oxide such as magnesium oxide, or a mixture thereof.

Examples of the sulfur vulcanizing agent include an inorganic vulcanizing agent such as powder sulfur (S), insoluble sulfur (S), precipitated sulfur (S), colloid sulfur, etc., tetramethylthiuram disulfide (TMTD) Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine may be used, and other vulcanizing agents such as amine disulfide or polymer sulfur Etc. may be used.

Examples of the organic peroxide include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, 2,5- Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5- Butyl peroxybenzene peroxide, 3-bis (t-butylperoxypropyl) benzene, di-t-butylperoxy-diisopropylbenzene, t-butylperoxybenzene, -3,3,5-trimethylsiloxane, n-butyl-4,4-di-t-butylperoxyvalerate, or mixtures thereof.

It is preferable that the vulcanizing agent is included in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the raw material rubber because the raw rubber can be thermally and chemically stabilized with a suitable vulcanization effect.

The vulcanization accelerator is an accelerator for accelerating the vulcanization rate or accelerating the retarding action in the initial vulcanization step. Specific examples thereof include a sulfenamide type, a thiazole type, a thiuram type, a thiourea type, a guanidine type, An aldehyde-amine-based compound, an aldehyde-ammonia-based compound, an imidazoline-based compound, a xanthate-based compound, or a mixture thereof.

Examples of the sulfenamide type vulcanization accelerator include N-cyclohexyl-2-benzothiazyl sulfenamide (CBS), N-tert-butyl-2-benzothiazyl sulfenamide (TBBS), N, N-dicyclohexyl 2-benzothiazyl sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, and mixtures thereof.

Examples of the thiol-based vulcanization accelerator include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole, zinc salt of 2-mercaptobenzothiazole , A copper salt of 2-mercaptobenzothiazole, a cyclohexylamine salt of 2-mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- Ethyl 4-morpholinothio) benzothiazole, and mixtures thereof.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylthiuram disulfide, dipentamethylthiuram monosulfide, dipentamethylene Thiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, or a mixture thereof, and the like.

Examples of thiourea vulcanization accelerators include thiacarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, diorthotolyl thiourea, and mixtures thereof.

Examples of the guanidine-based vulcanization accelerator include diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and mixtures thereof.

Examples of the dithiocarbamate-based vulcanization accelerator include zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamidithiocarbamate, zinc dipropyldithiocarbamate, complexation of zinc with piperidinedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, octadecyl Isopropyl dithiocarbamic acid zinc zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, penta methylenedithiocarbamate, sodium selenium dimethyldithiocarbamate, diethyldithiocarbamate, sodium diethyldithiocarbamate, Cadmium dithiocarbamate, or a mixture thereof.

Examples of the aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator include aldehyde-amine-based or aldehyde-ammonia-based reactants such as acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde- Compounds.

Examples of imidazoline vulcanization accelerators include imidazoline compounds such as 2-mercaptoimidazoline. Examples of the xanthate vulcanization accelerator include xanthate-based compounds such as zinc dibutylxanthogenate Compounds.

It is preferable that the vulcanization accelerator is included in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity improvement and rubber property enhancement through vulcanization speed promotion.

The vulcanization accelerating assistant may be an inorganic vulcanization accelerator aid, an organic vulcanization accelerator aid, or a mixture thereof, which is used in combination with the vulcanization accelerator to complete its promoting effect.

Examples of the inorganic vulcanization accelerator include zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and mixtures thereof. Examples of the organic-based vulcanization accelerating aids include stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof or mixtures thereof .

In the case where a mixture of zinc oxide and stearic acid is used as the vulcanization accelerator, zinc oxide is dissolved in stearic acid to form an effective complex with the vulcanization accelerator to produce favorable sulfur during the vulcanization reaction, thereby facilitating the crosslinking reaction of the rubber So that it can be more preferable. When a mixture of zinc oxide and stearic acid is used, 0.1 to 5 parts by weight of the mixture may be preferably used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the raw rubber to serve as a proper vulcanization accelerator.

The softening agent is used for imparting plasticity to the rubber to facilitate processing and reduce the hardness of the vulcanized rubber, and means a processing oil used for rubber compounding or rubber production. The softener may be a petroleum oil, a vegetable oil, or a mixture thereof.

Examples of the petroleum-based oil include paraffin-based oil, naphthene-based oil, aromatic-based oil, and the like.

Examples of the paraffin oil include P-1, P-2, P-3, P-4, P-5 and P-6 of Mychang Oil Co., N-1, N-2 and N-3 of Kokai Co., Ltd., and representative examples of the aromatic oils include A-2 and A-3 of Mingchang Oil Co.,

However, it is known that when the content of Polycyclic Aromatic Hydrocarbons (hereinafter referred to as 'PAHs') contained in the aromatic oil is 3 wt% or more together with the increase of environmental consciousness, Treated distillate aromatic extract (TDAE) oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil or heavy knife tent oil may be preferable, and the total content of PAHs component , A TDAE oil having a kinematic viscosity of at least 95 ° C. (210 ° F. SUS), an aromatic component in the softener of 15 to 25 wt%, a naphthene component of 27 to 37 wt%, and a paraffin component of 38 to 58 wt% . The TDAE oil has favorable properties for environmental factors such as low temperature property and fuel efficiency performance of the rubber composition including TDAE oil and possibility of cancer induction of PAHs.

Examples of the vegetable oils include vegetable oils such as castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, cone oil, rice bran oil, safflower oil, sesame oil, , Jojoba oil, macadamia nut oil, four flower oil, or tung oil.

It is preferable that the softener is used in an amount of 1 to 50 parts by weight based on 100 parts by weight of the raw rubber, because it improves the workability of the raw rubber.

On the other hand, the antioxidant is an additive used for stopping the chain reaction in which the tire is autoxidized by oxygen. Examples of the antioxidant include an amine type, a phenol type, a quinoline type, an imidazole type, a carbamic acid metal salt, a wax or a mixture thereof.

Examples of the amine type antioxidant include N-phenyl-N '- (1,3-dimethyl) -p-phenylenediamine, N- (1,3-dimethylbutyl) -N'- Phenyl-N'-isopropyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, -Cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine or a mixture thereof.

Examples of the phenolic antioxidant include phenol-based 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'- isobutylidene- , 6-di-t-butyl-p-cresol or mixtures thereof.

Examples of the quinoline antioxidant include 2,2,4-trimethyl-1,2-dihydroquinoline or derivatives thereof, and more specifically, 6-ethoxy-2,2,4-trimethyl- Dihydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline or mixtures thereof And the like.

Examples of the wax include waxy hydrocarbons and the like.

Considering such conditions that the solubility of the antioxidant in addition to the antioxidation action is high, the solubility in the rubber is small, the volatility thereof is small, the solvent should be inactive to the rubber, and the vulcanization should not be inhibited. It may be preferable to use it as a part.

The pressure-sensitive adhesive further improves the tack performance between the rubber and the rubber and improves the physical properties of the rubber by improving the mixing properties, dispersibility and processability of other additives such as fillers.

As the pressure-sensitive adhesive, a natural resin-based pressure-sensitive adhesive such as a rosin-based resin or a terpene-based resin and a synthetic resin-based pressure-sensitive adhesive such as a petroleum resin, a coal tar, or an alkylphenolic resin can be used.

Examples of the rosin-based resin include rosin resin, rosin ester resin, hydrogenated rosin ester resin, derivatives thereof, and mixtures thereof. Examples of the terpene resin include terpene resins, terpene phenol resins, and mixtures thereof.

Examples of the petroleum resin include aliphatic resins, acid modified aliphatic resins, alicyclic resins, hydrogenated alicyclic resins, aromatic (C9) resins, hydrogenated aromatic resins, C5-C9 copolymer resins, styrene resins, styrene A copolymer resin, or a mixture thereof.

The coal tar may be a coumarone-indene resin.

The alkylphenol resin may be a p-tert-alkylphenol formaldehyde resin and the p-tert-alkylphenol formaldehyde resin may be a p-tert-butyl-phenol formaldehyde resin, p-tert-octylphenol formaldehyde or And mixtures thereof.

The pressure-sensitive adhesive may be used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the raw rubber. If the content of the pressure-sensitive adhesive is less than 0.5 parts by weight based on 100 parts by weight of the raw material rubber, there is a fear that the adhesive performance is deteriorated.

More specifically, the rubber composition for forming the first bladder part may contain 0.5 to 5 parts by weight, 0.1 to 3 parts by weight and 0.1 to 10 parts by weight, respectively, of the vulcanizing agent, the vulcanization accelerator and the anti- May be more preferable.

The rubber composition for forming the first bladder portion 10 for forming the first bladder portion 10 may be prepared by mixing the above components in accordance with a conventional method. During the finishing step in which the first step of thermo-mechanical treatment or kneading and the crosslinking system are mixed, specifically at a maximum temperature of 110 to 190 占 폚, preferably at a high temperature of 130 to 180 占 폚, typically less than 110 占 폚, And a second step of mechanical treatment at a low temperature of 40 to 100 DEG C, but the present invention is not limited thereto.

Meanwhile, the second bladder part 20 may be formed of a rubber composition for forming a normal tire vulcan bladder.

Specifically, the rubber composition for forming the second bladder part may be a raw rubber comprising at least one of natural rubber and synthetic rubber; Reinforcing filler; And optionally additives such as vulcanizing agents, vulcanization accelerators, vulcanization accelerators, anti-aging agents, softening agents, pressure-sensitive adhesives or coupling agents.

In the raw rubber, the natural rubber may be the same as described above.

The synthetic rubber may be at least one selected from the group consisting of styrene butadiene rubber (SBR), modified styrene butadiene rubber, butadiene rubber (BR), modified butadiene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, (NBR), modified nitrile butadiene rubber, chlorinated polyethylene rubber, styrene ethylene butylene styrene (SEBS) rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber, hyaluron rubber, chloroprene rubber , Ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzyl chloride styrene butadiene rubber, bromomethyl styrene butyl rubber, maleic styrene butadiene rubber, carboxylic styrene butadiene rubber, epoxy isoprene rubber, maleic ethylene propylene rubber, Acid nitrile butadiene and , Or bromo mineyi suited polyisobutyl isoprene-co-para-methylstyrene (brominated polyisobutyl isoprene-co-paramethyl styrene, BIMS), but the like, and the like. One of the above-mentioned synthetic rubbers alone or a mixture of two or more thereof may be used.

Among these synthetic rubbers, it is more preferable that the synthetic rubbers are selected from the group consisting of styrene butadiene rubber, polyisoprene rubber, butadiene rubber, butyl rubber, halogenated rubber, ethylene-propylene rubber and mixtures thereof.

On the other hand, the reinforcing filler which can be used for the rubber composition for forming the second bladder part may be selected from the group consisting of carbon black, silica, and mixtures thereof. Among them, Lt; / RTI >

The carbon black may be the same as described above, and may be included in an amount of 10 to 100 parts by weight based on 100 parts by weight of the raw rubber. If the content of the carbon black is less than 10 parts by weight, the reinforcing performance by the carbon black as a filler may be deteriorated. If the content is more than 100 parts by weight, the workability of the rubber composition may be deteriorated.

The additive may be selected from the group consisting of a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent, a softening agent, a pressure sensitive adhesive, a coupling agent and a mixture thereof.

Each of these additives is the same as that described above, and can be used in an appropriate amount depending on the purpose and purpose.

As described above, the bladder for vulcanizing tire according to the present invention improves the vulcanization degree of the finished tire by changing the thickness and profile of the bladder and supplying a uniform heat source to each gauge of the tire, So that the durability and the rotation resistance of the tire can be increased.

According to another aspect of the present invention, there is provided a tire manufactured using the bladder for vulcanizing a tire.

The method of manufacturing the tire is generally applicable to any method used in the manufacture of a tire except for using a bladder for vulcanizing a tire produced by using the rubber composition for forming the first and second bladder parts As such, detailed description is omitted here.

The tires may be automobile tires, racing tires, airplane tires, agricultural tires, off-the-road tires, truck tires or bus tires. Further, the tire may be a radial tire or a bias tire, and preferably a radial tire.

In the case of manufacturing a tire using the bladder for vulcanizing tire according to the present invention, by supplying a uniform heat source to each gauge of the tire, the vulcanization degree of the finished tire is improved and the rubber strength is increased to increase the durability and rotation resistance of the tire .

1 is a sectional view schematically showing a conventional green tire in which a conventional tire vulcanizing bladder is installed inside.
2 is a cross-sectional view schematically showing a green tire having a bladder for vulcanizing tire according to an embodiment of the present invention installed inside.
3 is a cross-sectional view schematically showing a bladder for vulcanizing a tire having a thickness varying according to the position in Test Example 2. Fig.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Preparation Example and Comparative Example: Preparation of rubber composition for forming first bladder part

Each composition was blended in a Banbury mixer in the composition as shown in the following Table 1 and then released at 150 캜 to prepare a rubber composition for forming a first bladder part. In Table 1, the content units of each component are parts by weight.

Comparative Example 1 Production Example 1 Production Example 2 Production Example 3 Production Example 4 Natural rubber (NR) 80 80 80 80 80 Butyl rubber 20 20 20 20 20 Carbon black (1) 20 20 20 20 20 Graphene (2-1) - One 3 5 - Graphene (2-2) - - - - 5 Sulfur powder 1.5 1.5 1.5 1.5 1.5 Vulcanization accelerators (3) 0.5 0.5 0.5 0.5 0.5 Antioxidants (4) 1.5 1.5 1.5 1.5 1.5

In Table 1,

Carbon black (1): Carbon black (N330) having an I ₂ adsorption value of 50 to 300 mg / g and a DBP adsorption amount of 80 to 200 ml /

Graphene (2-1): graphene having a surface area of 100 to 3,000 m ² / g

(2-2): graphene having a surface area of 100 to 3,000 m ² / g and a surface modified with aminobenzoic acid (weight ratio of graphene and aminobenzoic acid used in graphene modification = 80: 20)

Vulcanization promoting material (3): ZBEC ^® (Rheinchemie Co.)

Anti-aging agent (4): N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine.

Test Example 1: Evaluation of physical properties

The first bladder specimens were prepared using the compositions for forming first bladder parts prepared in Preparation Examples 1 to 3 and Comparative Example 1, and the prepared first bladder specimens were evaluated for hardness, modulus, elongation and thermal conductivity The physical properties were measured and evaluated in accordance with ASTM regulations. The results are shown in Table 2 below.

The hardness was measured using a Shore A durometer.

The 100% modulus (MPa) is measured with a tensile tester (manufactured by Instron) with the specimen cut into a dumbbell shape. The 100% modulus refers to the stress acting on the specimen when the specimen is stretched 100%.

300% modulus (MPa) is the tensile strength at 300% elongation, measured according to ISO 37 standard, and the higher the value, the better the strength properties, especially the tensile strength.

The elongation percentage (%) means elongation at break, and was measured by a method in which the strain value until the test piece was broken in a tensile tester in%.

The thermal conductivity (W / mK, 150 ° C) was measured by the Laser Flash method.

Comparative Example 1 Production Example 1 Production Example 2 Production Example 3 Production Example 4 Hardness (Shore A) 68 68 69 71 70 100% modulus
(MPa) 2.5 2.6 2.7 2.9 2.8 300% modulus
(MPa) 7.8 8.0 8.1 8.2 8.2 Elongation (%) 555 550 548 545 547 Thermal conductivity (W / mk) 0.352 0.380 0.421 0.519 0.508

As shown in Table 2, as the content of the graphene in the composition for forming the first bladder portion was increased, the thermal conductivity was increased without greatly decreasing the hardness and the modulus value.

Test Example  2: Property evaluation

As shown in FIG. 3, the bladder was designed to have a thickness as shown in Table 3 according to the position of the bladder.

Specifically, first bladder portions corresponding to portions a to c in the bladder shown in FIG. 3 were formed by using the composition for forming a first bladder produced in Production Examples 1 to 4, respectively, A bladder portion corresponding to portions d to f was formed using the bladder-forming composition prepared in Comparative Example 1 to prepare a bladder of the Example.

In order to compare the effects, the bladder of Comparative Example 2 was prepared using the composition for forming bladder prepared in Comparative Example 1, with the thicknesses shown in Table 3 below.

Blader location The bladder (mm) of Comparative Example 2 The bladder (mm) of Examples 1 to 4 a ' 3 to 10 3 to 5 b ' 3 to 8 3 to 5 c 3 to 6 2 to 4 d 3 to 6 10-20 e 5 to 10 10-20 f 5 to 15 5 to 10

3, the hardness, modulus, elongation, and viscoelastic properties of the rubber specimen of the tire tread heated via the bladder a were measured according to ASTM regulations, and the results are shown in Table 4 below. At this time, the rubber specimen of the tire tread portion was made of the rubber composition of Comparative Example 1.

Specifically, the hardness, 100% modulus and elongation percentage were measured and carried out in the same manner as in Test Example 1.

The tensile strength (MPa) was measured by the method of ASTM D 790, and the higher the value, the better the strength.

G ', G "and tan δ were measured under a frequency of 10 Hz at -60 ° C. to 60 ° C. in a 0.5% strain using a Rheometrics Dynamic Spectrometer (RDS) measuring instrument. Resistance and excellent low fuel consumption characteristics.

Comparative Example 2 Example 1 Example 2 Example 3 Example 4 3, the thickness (mm) of the bladder a ' 3 3 3 3 3 Tread Hardness (Shore A) 68 69 71 73 72 100% modulus (MPa) 6.6 6.9 7.2 7.3 7.3 Elongation (%) 220 215 209 201 204 Tensile Strength (MPa) 17.8 18.1 18.5 19.2 19.0 60 캜 tan δ 0.247 0.240 0.221 0.215 0.217

As shown in Table 4, as the content of graphene increased, the tensile strength increased and the tan δ at 60 캜 decreased.

3, the physical properties of the hardness, modulus, elongation and viscoelasticity of the rubber specimen of the tire sidewall heated via the bladder d portion having different gauges are measured in accordance with the ASTM related regulations, The results are shown in Table 5 below. At this time, the rubber specimen of the tire sidewall was made of the rubber composition of Comparative Example 1.

Comparative Example 2 Example 1 Example 2 Example 3 Production Example 4 The thickness (mm) of the bladder d position in Fig. 5 10 15 20 20 Sidewall Hardness (Shore A) 55 57 58 60 59 100% modulus (MPa) 1.9 2.0 2.2 2.4 2.3 Elongation (%) 538 530 525 521 522 60 캜 tan δ 0.191 0.188 0.184 0.177 0.179

As shown in Table 5, as the bladder's gauge became thicker, the strength of the sidewall increased, and it was confirmed that the rotation resistance was improved by decreasing tan? At 60 占 폚.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, Of the right.

10 First bladder
10a corresponding to the tread
10b, 10b 'Shoulder portion corresponding portion
20 second bladder
20a and 20a '
20b and 20b '
100 Green tires
200 Bladder for tire vulcanization

Claims (9)

A tread which is a rubber layer in contact with the road surface and a tread corresponding portion and a shoulder portion corresponding respectively to the tread and the shoulder in a tire including a shoulder portion, a sidewall and a bead portion sequentially extending from both sides of the tread A first bladder portion; And
And a second bladder portion including a side wall corresponding portion and a bead portion corresponding portion corresponding to the side wall and the bead portion of the tire,
Wherein the first bladder portion is formed with a first bladder portion comprising 10 to 20 parts by weight of carbon black and 1 to 5 parts by weight of graphene based on 100 parts by weight of raw rubber containing at least one of natural rubber and butyl rubber ≪ / RTI >
Wherein the graphene has a surface area of 100 to 3,000 m < 2 > / g and the surface is modified with aminobenzoic acid,
Wherein the first bladder portion has a thickness thinner than the thickness of the second bladder portion. The method according to claim 1,
Wherein the first bladder portion has a thickness of 2 to 5 mm and the second bladder portion has a thickness of 5 to 20 m but the first bladder portion is thinner than the thickness of the second bladder portion, . The method according to claim 1,
And the thickness tends to increase toward the shoulder portion corresponding portion, the tread corresponding portion, the bead portion corresponding portion, and the side wall corresponding portion. The method according to claim 1,
Wherein the tread corresponding portion has a thickness of 3 to 5 mm, the shoulder portion corresponding portion has a thickness of 2 to 3 mm, the side wall corresponding portion has a thickness of 10 to 20 mm, and the bead portion corresponding portion has a thickness of 5 to 10 mm. The method according to claim 1,
Wherein said raw material rubber comprises 70 to 90 parts by weight of natural rubber and 10 to 30 parts by weight of butyl rubber. delete The method according to claim 1,
Wherein the carbon black has an iodine (I ₂ ) adsorption value of 50 to 300 mg / g and a dibutyl phthalate adsorption amount of 80 to 200 ml / 100 g. The method according to claim 1,
Wherein the rubber composition for forming the first bladder part further comprises 0.5 to 5 parts by weight of a vulcanizing agent, 0.1 to 3 parts by weight of a vulcanization accelerator, and 0.1 to 10 parts by weight of an antioxidant, based on 100 parts by weight of the raw rubber . A tire produced by using the bladder for tire vulcanization according to any one of claims 1 to 5, 7, and 8.

Images