KR101709558B1 - Rubber composition for tire case compound and tire manufactured by using the same - Google Patents

Abstract

The present invention relates to a rubber composition for tire case compound, and to a tire produced by using the same. To this end, the rubber composition for tire case compound comprises: 100 parts by weight of raw rubber; 5-40 parts by weight of a phenolic hydrocarbon resin whose weight average molecular weight ranges from 5,000 to 15,000 g/mol; and 1-10 parts by weight of a methylene donor. According to the present invention, it is possible to increase rolling resistance performance and hardness of tires.

Description

TECHNICAL FIELD [0001] The present invention relates to a rubber composition for a tire case compound, and a tire produced using the same. BACKGROUND ART [0002]

The present invention relates to a rubber composition for a tire case compound and a tire manufactured using the same. More particularly, the present invention relates to a rubber composition for a tire case compound, which improves rolling resistance performance and hardness characteristics of a bead filler rubber in order to improve the performance of a tire bead contacting a rim ≪ / RTI >

Tire Case Compound Rubber is required to have higher rigidity and hardness than other rubber compounds in order to support the load of the vehicle which is transmitted to the rim when the rim is mounted on the tire. High rubber stiffness is required to prevent the phenomenon.

In order to improve the rigidity of such tire case compound rubber, generally, a method of increasing the hardness and rigidity of the rubber due to the cross linking between the phenolic resin and the methylene donor is used. When the resin and the methylene donor are used, The reinforcing effect tends to be reduced due to the action of the donor with other chemicals such as zinc, and when the content is high, the hardness of the rubber is increased but the heat resistance between the clay and the rubber is increased and the rolling resistance performance is lowered. There is a disadvantage in that the compounding property is poor and the tensile strength is low.

An object of the present invention is to provide a rubber composition for a tire case compound having improved rolling resistance performance and hardness characteristics of a bead filler rubber.

Another object of the present invention is to provide a tire manufactured using the rubber composition for tire case compound.

In order to achieve the above object, a rubber composition for a tire case compound according to an embodiment of the present invention comprises 100 parts by weight of a raw rubber, 5 parts by weight of a phenolic hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / To 40 parts by weight, and 1 to 10 parts by weight of a methylene donor.

The raw material rubber may be natural rubber.

The phenolic hydrocarbon resin may be a phenol formaldehyde resin modified with a high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more.

The high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more may be extracted from naphtha.

The phenol-based hydrocarbon resin may have a melting point of 80 to 150 ° C, a hydrocarbon content of 1 to 70% by weight, and a phenol group content of 30 to 99% by weight.

The methylene donor may be any one selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, and combinations thereof.

Wherein the rubber composition for tire case compound comprises 80 to 90 parts by weight of carbon black, 1 to 5 parts by weight of zinc oxide, 0.5 to 3 parts by weight of stearic acid, 0.5 to 3 parts by weight of an antioxidant, 0.5 to 3 parts by weight of an accelerator 0.5 To 3 parts by weight and sulfur 5 to 10 parts by weight.

The present invention also relates to a process for preparing a master batch by mixing 100 parts by weight of a starting rubber, 5 to 40 parts by weight of a phenol-based hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol, and 1 to 10 parts by weight of a methylene donor, A step of re-mixing 50 to 100 parts by weight of carbon black, 1 to 5 parts by weight of zinc oxide, 0.5 to 3 parts by weight of stearic acid, 0.5 to 3 parts by weight of an antioxidant, 0.5 to 3 parts by weight of an accelerator and 5 to 10 parts by weight of sulfur, The present invention also provides a method for manufacturing a rubber composition for a tire case compound.

The tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire case compound.

The rubber composition for tire case compound of the present invention can improve the rolling resistance performance and hardness characteristics of the bead filler rubber.

The rubber composition for a tire case compound of the present invention can improve the performance of a tire bead portion contacting a rim when mounted on a rim.

The rubber composition for a tire case compound of the present invention has a high rolling resistance performance, rigidity and hardness in comparison with rubber components of other parts, and can prevent bead separation phenomenon that may occur when the vehicle is traveling.

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

The rubber composition for a tire case compound according to an embodiment of the present invention comprises 100 parts by weight of a raw rubber, 5 to 40 parts by weight of a phenolic hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol, To 10 parts by weight.

1) Raw material rubber

The raw material rubber may be any one selected from the group consisting of natural rubber, synthetic rubber, and a combination thereof, and preferably 100 parts by weight of natural rubber may be used.

The natural rubber may be any known natural rubber, and the origin of the natural rubber is 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.

2) a weight average molecular weight of 5,000 to 15,000 g / mol sign  Phenolic  Hydrocarbon resin

The phenol-based hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol used in the present invention is modified by using a phenol formaldehyde resin with a high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more.

Conventional Phenolic Resin is a product formed by the combination of phenol and formaldehyde, whereas the phenol-based hydrocarbon resin according to the present invention is obtained by modifying a phenol formaldehyde resin with a high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more (modified).

The high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more is characterized in that it is extracted from naphtha.

As the phenol formaldehyde is denatured into a high molecular weight hydrocarbon resin, the high molecular weight hydrocarbon resin comprises a phenol group. As a result, the rolling resistance of the tire can be improved first.

Using the phenolic hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol, the amount of reinforcing resin used and the carbon black content can be reduced, and the carbon black content is lowered to lower the heat resistance between the carbon black and the rubber, The difference can be improved.

The phenol-based hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol preferably has a melting point of 80 to 150 ° C, a hydrocarbon content of 1 to 70% by weight, and a phenol group content of 30 to 99% by weight.

The phenol-based hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol is preferably included in an amount of 5 to 40 parts by weight based on 100 parts by weight of the raw rubber. If the amount of the hydrocarbon resin is less than 5 parts by weight, a problem may arise in the reinforcing property. If the amount is less than 40 parts by weight, there is a disadvantage in heat generation.

3) Methylene donor

The methylene donor may be one selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, and combinations thereof, and hexamethoxymethylmelamine is most preferable.

The rubber composition containing the hydrocarbon resin hardly influences mixing or processing at the time of processing, but it is preferable that the methoxy group of the methylene donor at the time of vulcanization is higher than the hydroxyl group (-OH) of the high molecular weight phenolic phenolic hydrogen carbonate And reacts to form a methylene bridge between the melamine structure and the reinforcing resin to create a thermosetting resin network.

The methylene donor is preferably contained in an amount of 1 to 10 parts by weight based on 100 parts by weight of the raw material rubber. If the amount of the hydrocarbon resin is less than 1 part by weight, a problem may arise in the reinforcing property. If the amount is less than 10 parts by weight, unreacted material may be generated, which may cause a problem in vulcanization.

4) Other additives

The rubber composition for a tire case compound may further include various additives such as an additional vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, a filler, a coupling agent, or an anti-aging agent. The above various additives can be used as long as they are commonly used in the field to which the present invention belongs. The content thereof is not particularly limited as long as it depends on the compounding ratio used in a rubber composition for a tire case compound.

The rubber composition for the tire case compound may further include a filler. The filler may be any one selected from the group consisting of carbon black, silica, calcium carbonate, clay (hydrated aluminum silicate), aluminum hydroxide, lignin, silicate, talc, and combinations thereof, preferably carbon black.

The carbon black may have a nitrogen surface area per gram (N 2 SA) of 100 to 400 m 2 / g and a hydrogen ion index of 4 to 12. If the nitrogen adsorption specific surface area of the carbon black exceeds 400 m < 2 > / g, the workability of the rubber composition for a tire may deteriorate. If it is less than 100 m < 2 > / g, the reinforcing performance by carbon black as a filler may be deteriorated. If the DBP oil absorption of the carbon black exceeds 180 cc / 100 g, the workability of the rubber composition may deteriorate. If the DBP oil absorption is less than 60 cc / 100 g, the reinforcing performance of carbon black as a filler may be deteriorated.

The carbon black used in the present invention is preferably a product having a particle size distribution D50 / M of less than 0.7. When the particle size distribution D50 / M is 0.7 or more, the particle size distribution is large and the hardness may be lowered.

The content of the carbon black is preferably 80 to 90 parts by weight based on 100 parts by weight of the raw rubber.

If the content of the carbon black is less than 80 parts by weight, the reinforcing effect by the added carbon black can not be sufficiently obtained. If the content exceeds 90 parts by weight, the dispersibility and the physical properties may decrease due to the poor mixing in the rubber.

The rubber composition for a tire case compound may further comprise a coupling agent.

Examples of the coupling agent include a sulfide-based silane compound, a mercapto-based silane compound, a vinyl-based silane compound, an amino-based silane compound, a glycidoxine clock silane compound, a nitro- based silane compound, a chlorosilicate compound, a methacrylic silane compound, May be used, and a sulfide-based silane compound may be preferably used.

The sulfide-based silane compound is preferably selected from the group consisting of bis (3-triethoxysilylpropyl) tetrasulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, bis (4-trimethoxysilylbutyl) tetrasulfide, bis (3-triethoxysilylpropyl) trisulfide, bis Bis (3-trimethoxysilylethyl) trisulfide, bis (4-triethoxysilylethyl) trisulfide, bis (4-trimethoxysilylbutyl) trisulfide, bis (3-triethoxysilylbutyl) disulfide, bis (4-triethoxysilylbutyl) disulfide, bis 3-trimethoxysilylpropyl) disulfide, bis (2-trimethoxy Triethoxysilylbutyl) disulfide, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-triethoxysilylpropyl-N, N-dimethyl 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 2-trimethoxysilylethyl-N, N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl 3-trimethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, and combinations thereof may be used in combination with at least one compound selected from the group consisting of benzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzothiazole tetrasulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, And the like.

The mercaptosilane compound may be at least one selected from the group consisting of 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, May be any one selected from the group consisting of

The vinyl-based silane compound may be any one selected from the group consisting of ethoxysilane, vinyltrimethoxysilane, and combinations thereof.

The amino-based silane compound is preferably selected from the group consisting of 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- Methoxysilane, and a combination thereof.

The glycidoxime silane compound is preferably selected from the group consisting of? -Glycidoxypropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropylmethyldiethoxysilane,? -Glycidoxypropylmethyldimethoxysilane And a combination thereof.

The nitro-based silane compound may be any one selected from the group consisting of 3-nitropropyltrimethoxysilane, 3-nitropropyltriethoxysilane, and combinations thereof.

The chloro-based silane compound is selected from the group consisting of 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 2-chloroethyltrimethoxysilane, 2-chloroethyltriethoxysilane, and combinations thereof Lt; / RTI >

The methacrylic silane compound may be any one selected from the group consisting of? -Methacryloxypropyltrimethoxysilane,? -Methacryloxypropylmethyldimethoxysilane,? -Methacryloxypropyldimethylmethoxysilane, and combinations thereof Lt; / RTI >

The coupling agent may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the raw rubber for improving dispersibility of the silica. If the content of the coupling agent is less than 1 part by weight, improvement in dispersibility of silica may be insufficient, resulting in deterioration of rubber workability and lowering of fuel consumption performance. When the amount exceeds 20 parts by weight, interaction between silica and rubber is too strong, May be excellent, but the braking performance may be very poor.

The rubber composition for the tire case compound may further comprise a vulcanization accelerator.

The vulcanization accelerator refers to an accelerator that promotes the vulcanization rate or accelerates the retardation in the initial vulcanization step.

Examples of the vulcanization accelerator include sulfenamide, thiazole, thiuram, thiourea, guanidine, dithiocarbamate, aldehyde-amine, aldehyde-ammonia, imidazoline, Or a combination 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-oxydiethylene-2-benzothiazyl sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, and combinations thereof Based compound can be used.

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 combinations thereof. The thiazole-based compound may be used alone or in combination of two or more thereof.

Examples of the thiuram-based vulcanization accelerator include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide, tetramethylthiuram monosulfide, dipentamethylthiuram disulfide, dipentamethylthiuram monosulfide, dipentamethylene Any one of thiuram-based compounds selected from the group consisting of thiuram tetrasulfide, dipentamethylenethiuram hexasulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, and combinations thereof can be used.

Examples of the thiourea vulcanization accelerator include thiourea compounds selected from the group consisting of thiacarbamide, diethyl thiourea, dibutyl thiourea, trimethyl thiourea, diorthotolyl thiourea, and combinations thereof. Compounds may be used.

Examples of the guanidine-based vulcanization accelerator include guanidine-based compounds selected from the group consisting of diphenyl guanidine, diorthotolyl guanidine, triphenyl guanidine, orthotolyl biguanide, diphenyl guanidine phthalate, and combinations 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, and combinations thereof. The dithiocarbamic acid-based compound may be used alone or in combination of two or more thereof.

Examples of the aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator include aldehyde selected from the group consisting of acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde- -Amine-based or aldehyde-ammonia-based compounds may be used.

As the imidazoline-based vulcanization accelerator, for example, an imidazoline-based compound such as 2-mercaptoimidazoline can be used. Examples of the xanthate vulcanization accelerator include xanthates such as zinc dibutylxanthogenate Compounds may be used.

The vulcanization accelerator may be added in an amount of 0.5 to 4 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity improvement and rubber property improvement by accelerating vulcanization speed.

The vulcanization accelerating assistant may be any one selected from the group consisting of an inorganic vulcanization accelerator aid, an organic vulcanization accelerator aid, and a combination thereof, which is used in combination with the vulcanization accelerator to complete the promoting effect thereof .

As the inorganic vulcanization accelerating aid, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide and combinations thereof may be used have. As the organic vulcanization accelerating auxiliary, there may be selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, Can be used.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerating assistant. In this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, Thereby facilitating the crosslinking reaction of the rubber.

When the zinc oxide and the stearic acid are used together, they may be used in an amount of 1 to 5 parts by weight and 0.5 to 3 parts by weight, respectively, based on 100 parts by weight of the raw rubber to serve as a proper vulcanization accelerator. If the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate may be slow and the productivity may be deteriorated. If the content exceeds the above range, the scorch phenomenon may occur and the physical properties may be deteriorated.

The antioxidant is an additive used for stopping the chain reaction in which the tire is automatically oxidized by oxygen, and specifically includes an amine type, a phenol type, a quinoline type, an imidazole type, a carbamic acid metal salt, a wax, Can be used.

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 , N, N'-diaryl-p-phenylenediamine, N-phenyl-N'-cyclohexyl p-phenylenediamine or N-phenyl-N'-octyl- , One of them alone or a mixture of two or more thereof may be used.

Examples of the phenolic antioxidant include phenol-based 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis (4,6-dimethylphenol) 2,6-di-t-butyl-p-cresol, and the like, alone or in a mixture of two or more.

As the quinoline antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and its derivatives can be used. Specifically, 6-ethoxy-2,2,4-trimethyl- Dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, or poly (2, (2,2,4-trimethyl-1,2-dihydroquinoline, RD), and a mixture of two or more of them may be used. .

As the wax, waxy hydrocarbons may preferably be used.

Among the above-mentioned compounds, in consideration of the remarkable improvement effect of the use of the antioxidant, it is preferable to use N- (1,3-dimethylbutyl) -N'-phenyl- -p-phenylenediamine, poly (2.2.4-trimethyl-1,2-dihydroquinoline) or mixtures thereof may be more preferred.

Considering that the above-mentioned anti-aging agent is required to have high solubility in rubber, low volatility, inactivity with respect to rubber, and no inhibition of vulcanization, the anti-aging agent is preferably added in an amount of 0.5 To 3 parts by weight.

Also, the rubber composition for the tire case compound may include a vulcanizing agent. As the vulcanizing agent, a sulfur vulcanizing agent can be preferably used. The sulfur vulcanizing agent is 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 can be used. As the sulfur vulcanizing agent, a vulcanizing agent which produces elemental sulfur or sulfur, for example, amine disulfide, polymer sulfur and the like can be used.

It is preferable that the vulcanizing agent is included in an amount of 5 to 10 parts by weight based on 100 parts by weight of the raw rubber, from the viewpoint that the raw rubber is less sensitive to heat and chemically stable.

5) Manufacturing method

The tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire case compound.

The rubber composition for a tire case compound can be produced through a two-step continuous manufacturing process.

5 to 40 parts by weight of a phenol-based hydrocarbon resin having a weight average molecular weight of 5,000 to 15,000 g / mol, and 1 to 10 parts by weight of a methylene donor are mixed to prepare a master batch, A second step of reusing 80 to 90 parts by weight of black, 1 to 5 parts by weight of zinc oxide, 0.5 to 3 parts by weight of stearic acid, 0.5 to 3 parts by weight of an antioxidant, 0.5 to 3 parts by weight of an accelerator and 5 to 10 parts by weight of sulfur, Can be prepared in a suitable mixer.

The mixing conditions may be carried out at a temperature of 90 to 150 DEG C and a pressure of 4 to 10 kgf / cm < 2 >.

The rubber composition for the tire case compound may be used to support the load of the vehicle which is transmitted to the rim when the rim is mounted on the tire. The rubber composition for a tire case compound according to the present invention has a high rolling resistance performance, rigidity and hardness in comparison with rubber parts of other parts, and can prevent bead separation phenomenon that may occur when the vehicle is traveling.

A tire according to another embodiment of the present invention is manufactured using the rubber composition for the tire case compound. The method of manufacturing a tire using the rubber composition for a tire case compound may be any method conventionally used for manufacturing a tire, and a detailed description thereof will be omitted herein.

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.

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.

[ Manufacturing example : Preparation of rubber composition]

Rubber compositions for tire case compounds according to the following Examples and Comparative Examples were prepared using the compositions shown in Table 1 below. The rubber composition was prepared in the following two steps: a first step of preparing a masterbatch and a second step of adding and mixing other additives.

Mixing step Configuration Example Comparative Example One 2 3 4 5 One 2 3 Step 1: Master batch manufacturing Natural Rubber (1) 100 100 100 100 100 100 - 100 Polymeric phenolic resin (2) 5 10 20 30 40 5 - - Phenolic resin (3) - - - - - - - 5 Methylene donor (4) 1.0 2.0 4.0 6.0 10.0 - - 1.0 Step 2: Redistribution Natural Rubber (1) - - - - - - 100 - Polymeric phenolic resin (2) - - - - - - 5 - Methylene donor (4) - - - - - - 1.0 - Carbon black (5) 85 85 85 85 85 85 85 85 Zinc oxide 5 5 5 5 5 5 5 5 Stearic acid 2 2 2 2 2 2 2 2 Antioxidants (6) One One One One One One One One Promoters (7) 2 2 2 2 2 2 2 2 Sulfur (8) 7 7 7 7 7 7 7 7

(Unit: parts by weight)

(1) Natural rubber: TSR-20 grade (technically specified rubber-20), Wallace Plasticity (Po) 35, Plasticity Retention Index (PRI) 72, Mooney viscosity

(2) Polymer phenolic hydrocarbon resin: A hydrocarbon resin having a weight average molecular weight of 10,000 g / mol and a phenolic group content of 35%, prepared by modifying a phenolic resin with a hydrocarbon resin having a weight average molecular weight of 8,500 g / mol extracted from naphtha Suzy

(3) Phenolic resin: Straight Phenolic Resin (manufactured by Allnex)

(4) Methylene donor: Hexamethoxymethylmelamine (HMMM)

(5) Carbon black: Carbon black having a BET of 100 m < 2 > / g and a particle size distribution D50 / M of 0.7

(6) Anti-aging agent: 1,2-dihydroquinoline

(7) Accelerator: N, N dimethylcyclohexylammonium dibutyl dithiocarbamate (N, N Dimethyl Cyclohexyl Ammonium Dibutyl Dithiocarbamate)

(8) Sulfur: Insoluble sulfur

[ Experimental Example : Measurement of physical properties of the prepared rubber composition]

The physical properties of the rubber specimens prepared in the Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.

(1) Michalu Mooney Viscosity: Measured using a Mooney MV2000 (Alpha technology) device at a large rotor, preheating for 1 minute, rotor operating time of 4 minutes, and temperature at 125 占 폚.

(2) Scorch Stability: The scorch time is a measure of the time taken to rise 5 points from the minimum value of the Mooney, indicating that the longer the scorch stability is, the better.

(3) Hardness: ASTM Shore A hardness was measured after 1 hour in a temperature controllable combustion chamber. The Shore A hardness scale has an equal scale from 1 to 100. The larger the value, the harder the braking performance is.

(4) 300% Modulus (kgf / cm2): The dumbbell type having a length of 100 mm, an outer width of 25 mm and an inner width of 5 mm was used as a specimen and the tensile strength at 300% elongation was measured according to ISO 37 standard. The higher the value, the better the strength.

(5) Elongation at break (%): The stress value in the tensile tester until the test piece is broken is expressed in%.

(6) tan? (60 占 폚): Measured using RDS (Rheo Dynamic Spectroscopy). tan? (60 占 폚) = (G "/ G ') where G' is the viscous modulus and G" is the elastic modulus. The lower the tan δ (60 ° C), the better the fuel efficiency

Example Comparative Example One 2 3 4 5 One 2 3 Micheal Mooney viscosity (125 ° C) (1) 69 73 75 74 75 60 67 69 Scorch stability (min) (2) 12.1 11.9 11.8 11.9 11.9 12.5 12.1 12.1 Seal
Properties Hardness (3) 71 74 76 75 76 61 69 72 300% modulus (kgf / ㎠) (4) 67 72 75 76 76 59 65 67 Elongation at Break (%) (5) 210 192 187 185 186 290 230 201 Tensile strength (kgf / cm2) (6) 187 193 199 200 199 165 180 192 Tan? 60 占 폚 (7) 0.21 0.23 0.26 0.27 0.26 0.17 0.21 0.23

Referring to Table 2, the rubber composition for a tire case compound prepared using a masterbatch containing a polymeric phenol-based hydrocarbon resin and a methylene donor showed a higher hardness than the rubber composition of Comparative Example.

From the results in Table 2, it was confirmed in Comparative Example 1 and Example 1 that the reinforcing effect of the rubber composition was improved by using the methylene donor.

Comparative Example 1, which does not contain a methylene donor, and Comparative Example 2, which is a conventional tire manufacturing method, rather than a two-stage preparation method of rearranging after masterbatching, showed the lowest hardness. In contrast, the methylene donor- Examples 1 to 5 showed that the methylene donor tended to maximally react with the polymeric phenol-based hydrocarbon resin to improve the hardness even in the same parts by weight. Also, the results of confirming the low rotational resistance (LRR) were able to confirm the level without braking.

The properties of the polymeric phenolic hydrocarbon resin according to the weight change were confirmed through Examples 1 to 5. As a result, the optimum point could be confirmed at 5 to 20 parts by weight, and the reinforcing property of Example 3 including 20 parts by weight was the most excellent, and Example 2 including 10 parts by weight had both excellent reinforcement and rolling resistance .

Comparing the experimental results of Example 1 and Comparative Example 3, the reinforcing effect of the polymer phenolic hydrocarbon resin compared with the general phenolic resin was somewhat reduced, but the evaluation of the viscoelasticity revealed that the use of the polymer phenolic hydrocarbon resin in the case of tan? And the LRR (low rotational resistance) performance is increased.

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.

Claims (9)

100 parts by weight of the raw rubber,
5 to 40 parts by weight of a phenolic hydrocarbon resin having a weight average molecular weight of 10,000 to 15,000 g / mol, and
1 to 10 parts by weight of methylene donor
The phenolic hydrocarbon resin is obtained by modifying a phenol formaldehyde resin with a high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more,
Wherein the phenolic hydrocarbon resin has a melting point of 80 to 150 DEG C, a hydrocarbon content of 1 to 70 wt%, and a phenol group content of 30 to 99 wt%
Rubber composition for tire case compound. The method according to claim 1,
Wherein the raw material rubber is a natural rubber. delete The method according to claim 1,
Wherein the high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more is extracted from naphtha. delete The method according to claim 1,
Wherein the methylene donor is any one selected from the group consisting of hexamethylenetetramine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, and combinations thereof. The method according to claim 1,
Wherein the rubber composition for tire case compound comprises 80 to 90 parts by weight of carbon black, 1 to 5 parts by weight of zinc oxide, 0.5 to 3 parts by weight of stearic acid, 0.5 to 3 parts by weight of an antioxidant, 0.5 to 3 parts by weight of an accelerator 0.5 And 3 to 5 parts by weight of sulfur, based on 100 parts by weight of the rubber composition. 5 to 40 parts by weight of a phenol-based hydrocarbon resin having a weight average molecular weight of 10,000 to 15,000 g / mol, and 1 to 10 parts by weight of a methylene donor are mixed to prepare a master batch, and
50 to 100 parts by weight of carbon black, 1 to 5 parts by weight of zinc oxide, 0.5 to 3 parts by weight of stearic acid, 0.5 to 3 parts by weight of an antioxidant, 0.5 to 3 parts by weight of an accelerator and 5 to 10 parts by weight of sulfur are re- ≪ / RTI >
The phenolic hydrocarbon resin is obtained by modifying a phenol formaldehyde resin with a high molecular weight hydrocarbon resin having a weight average molecular weight of 5,000 g / mol or more,
Wherein the phenolic hydrocarbon resin has a melting point of 80 to 150 DEG C, a hydrocarbon content of 1 to 70 wt%, and a phenol group content of 30 to 99 wt%
A method for manufacturing a rubber composition for a tire case compound. A tire produced by using the rubber composition for a tire case compound according to any one of claims 1, 2, 4, 6, and 7.