KR20210045230A - Tire rubber composition with alky phosphate and tire manufactured from same - Google Patents

Abstract

Provided are a tire rubber composition comprising an alkyl phosphate having 1 to 60 carbon atoms, a tire manufactured therefrom, and the like. A tire using the tire rubber composition according to an embodiment of the present invention has excellent low-temperature characteristics.

Description

Tire rubber composition with alky phosphate and tire manufactured from the same {Tire rubber composition with alky phosphate and tire manufactured from the same}

It relates to a tire rubber composition comprising an alkyl phosphate and a tire produced therefrom.

Characteristics of tire tread rubber include steering stability, ride comfort, fuel economy performance, snow performance, abrasion resistance, braking performance, and durability.

It would be desirable for a tire tread to have all of these characteristics, but these characteristics exhibit a trade-off relationship in which the characteristics are partially contradicted to each other, that is, when one characteristic is improved, the other characteristic decreases. Therefore, it is difficult to simultaneously improve the properties that are in a trade-off relationship.

For example, in general, when the low-temperature flexibility is improved, the wet gripping performance is deteriorated.

There is a need for a tire tread rubber composition that has excellent low-temperature characteristics and does not deteriorate wet grip performance.

One aspect is to provide a tire rubber composition that has excellent low-temperature characteristics and does not deteriorate wet grip performance.

Another aspect is to provide a tire made of the rubber composition.

According to one aspect,

A tire rubber composition is provided comprising a C ₁ -C _{60 alkyl phosphate.}

According to the other side,

A tire made of the tire rubber composition is provided.

A tire using the tire rubber composition according to an embodiment of the present invention exhibits excellent low-temperature characteristics and does not degrade wet grip performance.

1 is a view schematically showing the structure of a tire according to an embodiment of the present invention.

Hereinafter, a tire rubber composition and a tire manufactured from the tire rubber composition will be described in more detail in an exemplary embodiment.

Since the inventive idea disclosed in the present specification can apply various transformations and have various implementations, specific implementations are described in detail in the detailed description, and when necessary, specific implementations are illustrated in the drawings. Effects and features of the creative ideas of the present specification, and a method of achieving them will be apparent with reference to implementation examples described later in detail together with the drawings. However, the creative idea of the present specification is not limited to the embodiments disclosed below, but may be implemented in various forms.

In the following embodiments, terms such as first and second are not used in a limiting meaning, but are used for the purpose of distinguishing one component from another component.

In the following embodiments, expressions in the singular include plural expressions unless the context clearly indicates otherwise.

In the following embodiments, terms such as include or have means that the features or elements described in the specification are present, and do not preclude the possibility of adding one or more other features or elements in advance.

When one embodiment can be implemented differently, a specific process order may be performed differently from the described order. For example, two processes described in succession may be performed substantially simultaneously, or may be performed in an order opposite to the described order.

Hereinafter, if necessary, embodiments of the present invention will be described in detail with reference to the accompanying drawings, and when describing with reference to the drawings, identical or corresponding components are given the same reference numerals, and redundant descriptions thereof will be omitted. It should be.

In the drawings, components may be exaggerated or reduced in size for convenience of description. For example, the size and thickness of each component shown in the drawings are arbitrarily shown for convenience of description, and thus the creative ideas disclosed in the present specification are not necessarily limited to those shown.

Tire rubber composition according to one aspect may include a C ₁ -C ₆₀ alkyl phosphate.

The alkyl group of the C ₁ -C ₆₀ alkyl phosphate may be linear or branched. For example, the _{alkyl group of the C 1} -C ₆₀ alkyl phosphate may be branched.

According to an embodiment of the present invention, the C ₁ -C ₆₀ alkyl phosphate may have a structure represented by the following Formula 1:

<Formula 1>

In Formula 1, R ₁ to R ₃ each independently represent hydrogen or a C ₁ -C ₂₀ alkyl group, except when all of _{R 1} to R _{3 are hydrogen.}

For example, R ₁ to R ₃ are independently of each other hydrogen, methyl group, ethyl group, n -propyl group, isopropyl group, n -butyl group, sec -butyl group, isobutyl group, tert -butyl group, n -phen Tyl group, tert -pentyl group, neopentyl group, isopentyl group, sec -pentyl group, 3-pentyl group, sec -isopentyl group, n -hexyl group, isohexyl group, sec -hexyl group, tert -hexyl group, n -heptyl group, isoheptyl group, sec -heptyl group, tert -heptyl group, n -octyl group, isooctyl group, sec -octyl group, tert -octyl group, 2-ethylhexyl, n -nonyl group, isononyl group , sec -nonyl group, tert -nonyl group, n -decyl group, isodecyl group, sec-decyl group, or tert -decyl group.

According to an embodiment of the present invention, in Formula 1, R ₁ , R ₂ and R ₃ may all be the same substituent.

According to an embodiment of the present invention, the C ₁ -C ₆₀ alkyl phosphate may have a Tg of -110 to -100°C.

According to an embodiment of the present invention, the C ₁ -C ₆₀ alkyl phosphate may have a kinematic viscosity of 6.0 to 8.0 (@40°C)

According to an embodiment of the present invention, the alkyl phosphate of Formula 1 may be Compound 100:

In the structure of Compound 100, positions marked with * are chiral carbons as follows. Thus, the carbon may be S or R.

For example, in the compound 100, all carbons marked with * may be S. For example, in the compound 100, all carbons marked with * may be R. For example, carbons marked with * in the compound 100 may be S or R independently of each other.

According to one embodiment of the present invention, the tire rubber composition may include 1.00 to 20.0 parts by weight of _{the C 1} -C _{60 alkyl phosphate based on 100 parts by weight of the raw rubber.}

When the _{weight of the C 1} -C ₆₀ alkyl phosphate is less than 1.00 parts by weight, there is almost no low-temperature characteristic effect, and when it exceeds 20.0 parts by weight, wet grip performance may be deteriorated.

The rubber composition according to an embodiment of the present invention may include natural rubber and/or synthetic rubber. The natural rubber may be a general natural rubber or a modified natural rubber.

The general natural rubber may be used as long as it is known as natural rubber, and the country of origin is not limited. The natural rubber mainly contains cis-1,4-polyisoprene, but may contain trans-1,4-polyisoprene depending on required properties. Therefore, in addition to natural rubber containing cis-1,4-polyisoprene as a main body, the natural rubber includes trans-1,4-isoprene as a main body, such as Valata, a kind of rubber of the Sapota family from South America. It may also contain rubber.

The modified natural rubber means that the general natural rubber is modified or purified. For example, examples of the modified natural rubber include epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber.

According to one embodiment of the present invention, the synthetic rubber is at least selected from butadiene rubber, styrene butadiene rubber (SBR), isoprene-containing styrene butadiene rubber, nitrile-containing styrene butadiene rubber, neoprene rubber, chlorobutyl rubber, and bromobutyl rubber. It may contain one type.

According to one embodiment of the present invention, the rubber composition may include styrene-butadiene rubber and butadiene rubber as raw rubber.

According to an embodiment of the present invention, the styrene-butadiene rubber may be 30 to 70 parts by weight based on 100 parts by weight of the raw rubber, and the butadiene rubber may be 70 to 30 parts by weight.

According to one embodiment of the present invention, the rubber composition may include a filler, for example, may include silica or carbon black.

Any of the silicas generally known may be used, and for example, commercially available Z-175, US7000GR, or 9000GR may be used.

According to an embodiment of the present invention, the content of the silica may be 60 to 150 parts by weight based on 100 parts by weight of the raw rubber. When the silica content is in the constant range, the physical properties of the tread rubber are optimal.

The silica may have a nitrogen surface area per gram (N ₂ SA) of 100 to 180 m ² /g, and a specific surface area of CTAB (cetyl trimethyl ammonium bromide) adsorption of 110 to 170 m ² /g, The present invention is not limited thereto.

When the nitrogen adsorption specific surface area ^{of the silica is less than 100m 2} /g, the reinforcing performance by silica as a filler may be disadvantageous, and ^{when it exceeds 180m 2} /g, the processability of the rubber composition may be disadvantageous. In addition, when the CTAB adsorption specific surface area ^{of the silica is less than 110 m 2} /g, the reinforcing performance by silica as a filler may be disadvantageous, and ^{when it exceeds 170 m 2} /g, the processability of the rubber composition may be disadvantageous.

According to an embodiment of the present invention, the rubber composition may include a silane coupling agent to improve dispersion of silica. Any silane coupling agent may be used as long as it is conventionally used in the field to which the present invention belongs, and the content thereof is not particularly limited as it depends on the blending ratio used in the conventional tire tread rubber composition.

The carbon black may have a nitrogen surface area per gram (N ₂ SA) of 30 to 300 m ² /g, and an oil absorption of DBP (n-dibutyl phthalate) may be 60 to 180 cc/100 g, but the present invention This is not limited to this.

When the nitrogen adsorption specific surface area of the carbon black ^{exceeds 300 m 2} /g, the processability of the rubber composition for tires may be disadvantageous, and ^{when it is less than 30 m 2} /g, the reinforcing performance by carbon black as a filler may be disadvantageous. In addition, when the DBP oil absorption amount of the carbon black exceeds 180cc/100g, the processability of the rubber composition may be deteriorated, and when it is less than 60cc/100g, the reinforcing performance by carbon black as a filler may be disadvantageous.

Representative examples of the carbon black include 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.

According to one embodiment of the present invention, the carbon black content may be 40 to 55 parts by weight based on 100 parts by weight of the rubber composition. If the content of the carbon black is less than 40 parts by weight, the strength may not be satisfactory, and if it exceeds 55 parts by weight, the processability of the rubber composition may be disadvantageous.

According to one embodiment of the present invention, the rubber composition may not contain carbon black. That is, the rubber composition may contain only silica as a pillow.

According to one embodiment of the present invention, the rubber composition may be for a tire tread.

The tire tread rubber composition may optionally further include various additives such as an additional vulcanization agent, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent, an antioxidant, or a softener. Any of the various additives may be used as long as they are commonly used in the field to which the present invention belongs, and their content is not particularly limited, as it depends on the blending ratio used in a typical tire tread rubber composition.

As the vulcanizing agent, a sulfur-based vulcanizing agent can be preferably used. The sulfur-based vulcanizing agents include inorganic vulcanizing agents such as powdered sulfur (S), insoluble sulfur (S), precipitated sulfur (S), and colloidal sulfur, and tetramethylthiuram disulfide (TMTD), tetraethyl Organic vulcanizing agents such as tetraethyltriuram disulfide (TETD) and dithiodimorpholine may be used. As the sulfur vulcanizing agent, specifically elemental sulfur or a vulcanizing agent that produces sulfur, for example, amine disulfide, polymer sulfur, or the like may be used.

It is preferable that the vulcanizing agent be included in an amount of 0.5 to 10.0 parts by weight based on 100 parts by weight of the raw rubber, as an appropriate vulcanizing effect, and that the raw rubber is less sensitive to heat and is chemically stable.

The vulcanization accelerator refers to an accelerator that accelerates the vulcanization rate or accelerates the delaying action in the initial vulcanization step.

The vulcanization accelerators include sulfenamide-based, thiazole-based, thiuram-based, thiourea-based, guanidine-based, dithiocarbamic acid-based, aldehyde-amine-based, aldehyde-ammonia-based, imidazoline-based, xanthate-based and these Any one selected from the group consisting of combinations may be used.

Examples of the sulfenamide-based vulcanization accelerator include N-cyclohexyl-2-benzothiazylsulfenamide (CBS), N-tert-butyl-2-benzothiazylsulfenamide (TBBS), and N,N-dicyclohexyl Any one selected from the group consisting of -2-benzothiazylsulfenamide, N-oxydiethylene-2-benzothiazylsulfenamide, N,N-diisopropyl-2-benzothiazolesulfenamide, and combinations thereof Sulfenamide-based compounds of can be used.

Examples of the thiazole-based vulcanization accelerator include 2-mercaptobenzothiazole (MBT), dibenzothiazyl disulfide (MBTS), sodium salt of 2-mercaptobenzothiazole, and zinc salt of 2-mercaptobenzothiazole. , Copper salt of 2-mercaptobenzothiazole, cyclohexylamine salt of 2-mercaptobenzothiazole, 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-di Any one thiazole-based compound selected from the group consisting of ethyl 4-morpholinothio)benzothiazole and combinations thereof may be used.

Examples of the thiuram-based vulcanization accelerator include tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetramethyl thiuram monosulfide, dipentamethylene thiuram disulfide, dipentamethylene thiuram monosulfide, dipentamethylene Thiuram tetrasulfide, dipentamethylene thiuram hexasulfide, tetrabutyl thiuram disulfide, pentamethylene thiuram tetrasulfide, and any one thiuram-based compound selected from the group consisting of a combination thereof may be used.

As the thiourea-based curing accelerator, for example, any one thiourea-based selected from the group consisting of thiacarbamide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea, and combinations thereof Compounds can be used.

As the guanidine-based vulcanization accelerator, for example, any one guanidine-based compound selected from the group consisting of diphenylguanidine, diorthotolylguanidine, triphenylguanidine, orthotolylbiguanide, diphenylguanidine phthalate, and combinations thereof can be used. I can.

Examples of the dithiocarbamic acid-based vulcanization accelerator include zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, Zinc dibutyldithiocarbamate, zinc diamyldithiocarbamate, zinc dipropyldithiocarbamate, complex salt of zinc pentamethylenedithiocarbamate and piperidine, zinc hexadecylisopropyldithiocarbamate, octadecyl Zinc isopropyldithiocarbamate, zinc dibenzyldithiocarbamate, sodium diethyldithiocarbamate, piperidine pentamethylenedithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, dia Any one dithiocarbamic acid-based compound selected from the group consisting of cadmium mildithiocarbamate and combinations thereof may be used.

Examples of the aldehyde-amine-based or aldehyde-ammonia-based vulcanization accelerator include, for example, an aldehyde selected from the group consisting of acetaldehyde-aniline reactant, butylaldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde-ammonia reactant, and combinations thereof. -Amine-based or aldehyde-ammonia-based compounds can be used.

As the imidazoline-based vulcanization accelerator, an imidazoline-based compound such as 2-mercaptoimidazoline may be used, and as the xanthate-based vulcanization accelerator, for example, a xanthate-based zinc dibutylxanthogenate or the like can be used. Compounds can be used.

The vulcanization accelerator may be included in an amount of 0.5 to 4.0 parts by weight based on 100 parts by weight of the raw rubber in order to maximize productivity and rubber properties through acceleration of the vulcanization speed.

The vulcanization accelerator aid is a blending agent used in combination with the vulcanization accelerator to complete the accelerating effect, and any one selected from the group consisting of inorganic vulcanization accelerators, organic vulcanization accelerators, and combinations thereof may be used. .

As the inorganic vulcanization accelerator, any one selected from the group consisting of zinc oxide (ZnO), zinc carbonate, magnesium oxide (MgO), lead oxide, potassium hydroxide, and combinations thereof can be used. have. The organic vulcanization accelerator is selected from the group consisting of stearic acid, zinc stearate, palmitic acid, linoleic acid, oleic acid, lauric acid, dibutyl ammonium oleate, derivatives thereof, and combinations thereof. You can use any one of them.

In particular, the zinc oxide and the stearic acid may be used together as the vulcanization accelerator, and in this case, the zinc oxide is dissolved in the stearic acid to form an effective complex with the vulcanization accelerator, thereby reducing advantageous sulfur during the vulcanization reaction. It facilitates the crosslinking reaction of the rubber by making it.

When the zinc oxide and the stearic acid are used together, it may be used in an amount of 1 to 10 parts by weight and 0.5 to 3 parts by weight based on 100 parts by weight of the raw rubber, respectively, to serve as an appropriate vulcanization accelerator. When the content of the zinc oxide and the stearic acid is less than the above range, the vulcanization rate may be slow and thus productivity may decrease, and when the content of the zinc oxide and the stearic acid is less than the above range, a scorch phenomenon may occur and physical properties may be deteriorated.

The softening agent is added to the rubber composition to facilitate processing by imparting plasticity to the rubber or to reduce the hardness of the vulcanized rubber, and refers to oils and other materials used during rubber compounding or rubber production. The softener means process oil or oils included in other rubber compositions. As the softener, any one selected from the group consisting of petroleum oils, vegetable oils, and combinations thereof may be used, but the present invention is not limited thereto.

According to one embodiment of the present invention, the tire rubber composition may include 10 to 50 parts by weight of the process oil based on 100 parts by weight of raw rubber.

When the content of the processing oil is within the above range, processing of the tire rubber composition is easy and vulcanization properties are optimal.

As the petroleum oil, any one selected from the group consisting of paraffin oil, naphthenic oil, aromatic oil, and combinations thereof may be used.

Representative examples of the paraffinic oil include P-1, P-2, P-3, P-4, P-5, and P-6 of Michang Oil Co., Ltd., and a representative example of the naphthenic oil is Michang Oil. N-1, N-2, and N-3 of Co., Ltd. may be mentioned, and representative examples of the aromatic oil include A-2 and A-3 of Michang Oil Co., Ltd.

However, it is known that cancer-causing potential is high when the content of polycyclic aromatic hydrocarbons (hereinafter referred to as PAHs) contained in the aromatic oil is 3% by weight or more with the recent increase in environmental awareness, TDAE ( Treated distillate aromatic extract) oil, mild extraction solvate (MES) oil, residual aromatic extract (RAE) oil, or heavy naphthenic oil may be preferably used.

In particular, the oil used as the softener has a total content of PAHs of 3% by weight or less with respect to the entire oil, a kinematic viscosity of 95 or more (210°F SUS), an aromatic component in the softener of 15 to 25% by weight, a naphthenic component TDAE oil having 27 to 37% by weight and 38 to 58% by weight of the paraffinic component can be preferably used.

The TDAE oil is advantageous in terms of environmental factors such as cancer-causing potential of PAHs while improving low-temperature characteristics and fuel economy performance of tires including the TDAE oil.

The plant oils include castor oil, cottonseed oil, linseed oil, canola oil, soybean oil, palm oil, palm oil, peanut oil, pine oil, pine tar, tall oil, corn oil, rice bran oil, safflower oil, sesame oil, olive oil, sunflower oil, palm kernel oil, camellia oil , Jojoba oil, macadamia nut oil, saflower oil, tung oil, and any one selected from the group consisting of a combination thereof may be used.

The softening agent is preferably used in an amount of 0 to 10 parts by weight based on 100 parts by weight of the raw rubber in that it improves the processability of the raw rubber.

The anti-aging agent is an additive used to stop a chain reaction in which the tire is automatically oxidized by oxygen. As the anti-aging agent, any one selected from the group consisting of amine-based, phenol-based, quinoline-based, imidazole-based, carbamic acid metal salts, waxes, and combinations thereof may be appropriately selected and used.

Examples of the amine-based anti-aging agent include N-phenyl-N'-(1,3-dimethyl)-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-diaryl-p-phenylenediamine, N-phenyl-N' -Any one selected from the group consisting of cyclohexyl p-phenylenediamine, N-phenyl-N'-octyl-p-phenylenediamine, and combinations thereof may be used. The phenolic antioxidants include phenolic 2,2'-methylene-bis(4-methyl-6-tert-butylphenol), 2,2'-isobutylidene-bis(4,6-dimethylphenol), 2 ,6-di-t-butyl-p-cresol, and any one selected from the group consisting of combinations thereof may be used. As the quinoline-based antioxidant, 2,2,4-trimethyl-1,2-dihydroquinoline and derivatives thereof may be used, and specifically, 6-ethoxy-2,2,4-trimethyl-1,2-di Consisting of hydroquinoline, 6-anilino-2,2,4-trimethyl-1,2-dihydroquinoline, 6-dodecyl-2,2,4-trimethyl-1,2-dihydroquinoline, and combinations thereof Any one selected from the group can be used. Preferably, waxy hydrocarbon may be used as the wax.

In addition to the anti-aging effect, the anti-aging agent must have a high solubility in rubber, low volatility, and inert to rubber, and not inhibit vulcanization, etc., 1 to 10 parts by weight of the raw rubber. It may be included in parts by weight.

A typical amount of the antioxidant may be included in, for example, about 1 to about 5 parts by weight. Representative antioxidants are, for example, diphenyl-p-phenylenediamine and others, but are not limited thereto.

Referring to FIG. 1, the tire 10 includes a tread part 100, a sidewall part 200, and a bead part 300.

The tread portion 100 is a portion in contact with the ground in cross section, and serves to protect the tire from impact and trauma from the road surface. A plurality of blocks partitioned by grooves may be formed on the surface of the tread portion as described above to improve the drainage characteristics of the tire.

The rubber composition according to an embodiment of the present invention may be included in the tread.

The sidewall 200 and the bead 300 are sequentially positioned on both sides along the width direction of the tire with the tread portion as the center.

The sidewall 200 is a part that extends from both ends of the tread to form side surfaces of the tire, withstands continuously repeated contraction and expansion during driving, and protects the carcass layer 400 located on the inner surface. Do it.

The bead part 300 is provided at both ends of the sidewall 200 to surround the end of the cord paper, and the bead part 300 includes a bead core 500 including a ring-shaped steel wire. In addition, in the bead part 300, a rim cushion (not shown) is disposed at a portion in contact with the rim.

A carcass layer 400 is positioned between the pair of left and right bead portions 300, and is bonded to the tire rubber sheet inside the tire to form the skeleton of the tire, and the carcass layer 400 is the bead core 500 ) It is winding up from the inside of the tire to the outside.

An inner liner 700 is positioned on one side of the inner side of the carcass layer 400 and serves to prevent air inside the tire from escaping to the outside.

The belt layer 600 is positioned on the outer surface of the carcass layer 400 located on the tread part 100 as a reinforcing layer that increases the elasticity of the tread and has maneuverability and stability.

The belt layer rubber may include a cobalt compound, and the cobalt compound is a cobalt salt, a cobalt-boron ester, an organic acid cobalt salt, an inorganic acid cobalt salt, a non-cobalt salt, and the like, and as an adhesion system, cobalt salt alone, cobalt- In addition to RH and cobalt-HRH, resins (e.g., methylene acceptor: phenolic, resorcinol, cresol, etc., or donor: hexamethylenetetraamine (HMT), hexamethoxymethylmelamine (HMMA), pentamethoxymethyl) Melamine (PMMA)] modified adhesive system.

In general, to improve adhesion, improve the adhesion system of the adhesive compound rubber (cobalt-RH, cobalt-HRH, their modification system), improve the resin used as an adhesion aid and improve the performance, improve the cobalt salt used as the adhesion aid, adhesion Improvements in the vulcanization system of rubber and the use of new compounding compositions (reinforcing agents, carbon black, silica, polymers, and chemicals) are being used.

The content of the cobalt compound may include 0.2 to 5.0 parts by weight based on 100 parts by weight of the raw rubber, but is not limited thereto.

A cap ply 800 including a hybrid cord may be disposed between the belt layer 600 and the tread portion 100. The cap ply 800 may suppress the flow of the belt layer 600 while driving to maintain the performance of the tire.

The tire according to another embodiment of the present invention includes the step of using the tire rubber composition when forming a green tire. The method of forming a green tire using the tire rubber composition can be applied to any method as long as it is a method conventionally used for manufacturing a tire, and a detailed description thereof will be omitted in the present specification.

1 illustrates a tire for a passenger car, but is not limited thereto, and may be a tire for a passenger car, a tire for a race, an airplane tire, a tire for agricultural machinery, an off-the-road tire, a truck tire, a bus tire, etc. have. In addition, the tire may be a radial tire or a bias tire, preferably a radial tire.

The present invention will be described in more detail through the following examples and comparative examples. However, the examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

Example 1 and Comparative example 1, 2

Each of the components in Table 1 below was added to a Banbury mixer in the ratio (unit: parts by weight) and mixed. After all the ingredients were added to the Tangential type Banbury mixer, the ratio of each ingredient was adjusted so that the fill factor of 1.65L capacity was 0.65 to 0.70.

Comparative Example 1 is a rubber composition to which an alkyl phosphate is not added, and Comparative Example 2 is a rubber composition in which the BR content is increased to improve low temperature flexibility.

Comparative Example 1 Comparative Example 2 Example 1 SSBR ^{1 )} 72 65 72 BR ²⁾ 48 55 48 Silica ^{3 )} 120 120 120 Oil ^{4 )} 32 32 28 Alkyl phosphate ^{5 )} 0 0 4 Zinc oxide ^{6 )} 2.0 2.0 2.0 Stearic acid ^{7 )} 1.0 1.0 1.0 Accelerator ^{8 )} 1.8 1.8 1.8 Sulfur ^{9 )} 0.75 0.75 0.75

1) SLR4630　(Sloution Styren Butadiene Rubber), Styron

Styrene 25%, Vinyl 63%, Oil Content 37.5　phr, Mw 1,000,000,　Tg -28℃

2) CB25 (SLR4630　(Sloution Styren Butadiene Rubber), LG Chemical

Ash content 0.75 MAX, Raw Material Moonet Viscosity 42~52, 1,4-cis CONTENT 96MIN

3) Silica 5000 GR, Evonik

BET SURFACE AREA　115.0 ± 15.0　㎡/g, CTAB SURFACE AREA 110.0 ± 15.0㎡/g, pH 6.5 ± 0.8

4) RAE PLAXOLENE 50, TOTAL CHEMICAL

ACID NUMBER　1.0 MAX, FLASH　　POINT 210.0 MIN, KINEMATIC VISCOSITY (AT 100℃ ), 60.0 ± 20.0

5) TOP(tri-2-ethylhexyl phosphate), HANG ZHOU QIANYANG TECHNOLOGY CO., LTD

Appearance: Clear liquid

Density (g/cm3, @20℃): 0.921~927

Acid Value (mgKOH/g): 0.10 MAX

Purity (%): 99.0 MIN

2-ethyl hexanol (%): 0.10 MAX

Di(2-rthyl hexyl) Phosphate (%): 0.10 MAX

Water (%): 0.10 Max

6) Zinc Oxide (ZnO #2), DA LIAN ZINC

DENSITY　5.5 ± 0.1, HEATING LOSS 0.30 MAX, PURITY 99.0 MIN

7) STEARIC ACID (STEARINE G3), FACI SPA

ACID VALUE 204.0 ± 5.0, IODINE VALUE IODINE VALUE 1.0 MAX, MELTING POINT　 55.0 MIN

8) CBS, Puyang Willing

HEATING　　LOSS 0.30MAX, ASH　　CONTENT 0.30MAX, MELTING POINT 98.0-104.0, PURITY 94.0MIN

9) MIDAS-101(Normal sulur), MIWON CHEMICALS CO., LTD

INSOLUBLES IN CS2 0.50 MAX, OIL CONTENT 1.00 ± 0.20, PURITY　98.5 MIN

Evaluation example

Uncured Evaluation of rubber properties

The Mooney viscosity (ML1+4(10(TC)) of the tire rubber composition prepared in Table 1 was measured according to ASTM standard D1646 and shown in Table 2.

ML1+4 is a value representing the viscosity of the unvulcanized rubber, and the lower the value, the better the processability of the unvulcanized rubber.

Evaluation of vulcanized rubber properties

Each of the rubber compositions for tires prepared in Table 1 was press-cured in a mold (15cmХ15cmХ0.2cm) at 165°C for 10 minutes with a force of 100 tons to prepare vulcanized rubbers, respectively.

The hardness, 300% modulus, elongation, tensile strength, breaking strength, abrasion and viscoelasticity of each vulcanized rubber were measured in the following manner, and the results are shown in Table 2.

HD(hardness)

The hardness was measured by a shore A type hardness tester. Hardness indicates steering stability to the degree of hardness of the specimen, and the higher the value, the better the steering stability.

300% Modulus

The 300% modulus was measured according to ASTM standard D412 as the tensile strength at 300% elongation, and the higher the value, the better the strength.

Elongation

The elongation rate was measured by a method in which the strain value until the test piece breaks in a tensile tester is expressed in %.

Tensile properties

The measurement of the tensile strength of the crosslinked specimen was performed according to ASTM D412 using a tensile tester (INSTRON). The specimen for measurement was manufactured in a sheet form using a hydraulic press and a dumbbell type using a specimen cutter. Test conditions were measured at a tensile speed of 500 mm/min at room temperature. Tensile strength (T/S) is a value representing the stress value until the test piece is broken in a tensile testing machine, and the force received per unit area was measured.

Viscoelasticity

The viscoelasticity was measured by using a Gabo viscometer measuring instrument and measuring the Tanδ value from -80°C to 70°C under 10Hz frequency at 0.2% strain. At this time, the temperature having the highest Tanδ value is defined as the glass transition temperature, and the smaller the Tanδ value at 60°C, the less heat generated during driving and the better the rolling resistance.

Comparative Example 1 Comparative Example 2 Example 1 Mooney viscosity (100℃) 56 55 53 Mooney
Scorch Scorch time t10 19.6 19.3 20.5 Oscillating Disk Rheometer (ODR) t40 4.1 4.2 4.3 Hardness 60 60 59 300% modulus (kg/cm ² ) 79 74 69 Tensile strength (kg/cm ² ) 149 145 151 Elongation(%) 470 480 520 Tg (℃) -24.3 -25.1 -25.5 -30℃-E' 240 220 164 0℃-E" 7 4 7 60℃ tanδ 0.142 0.410 0.148

-30℃-E' is a value representing low-temperature characteristics, and it can be said that the lower the elastic modulus value, the better the low-temperature characteristics.

0°C-E" is a value representing the wet grip characteristics, and the higher the Loss Modulus value, the better the wet braking characteristics.

From the results of Table 2, it can be seen that Example 1 has better low-temperature characteristics than Comparative Examples 1 and 2. In addition, it can be seen that in the wet grip characteristics, Example 1 is equivalent to that of Comparative Example 1, and is superior to Comparative Example 2.

Tire manufacturing

Each tire was manufactured by applying the rubber compositions of Example 1 and Comparative Example 1 to the trebu region (Winter　Tire　195/65R15). For other parts of the tire, the materials and methods generally used in the above standard were applied.

Evaluation example

The tires of Example 1 and Comparative Example 1 were evaluated for handling performance, braking performance, and the like, and are shown in Table 3.

Item Comparative Example 1 Example 1 Proving Ground
Test Dry Handling (Average Rating) 6.35 6.48 Wet Handling (Average Rating) 5.96 6.20 Dry Braking (Distance) 46.6 47.6 Wet Asphalt Braking (Distance) 30.8 29.6 Winter Test Snow Handling (Average Rating) 6.65 6.58 Snow Braking (Distance) 17.5 17.2 ICE Braking (Distance) 21.7 21.6

Handling performance means that the higher the value is, the better it is, and the lower the value, the better the braking performance is.

From the results of Table 3, it can be seen that Example 1 is superior to Comparative Example 1 in terms of handling performance in Ground Test and Winter Test.

From the results of Table 3, it can be seen that Example 1 is superior to Comparative Example 1 in the case of wet asphalt breaking performance in the ground test.

Tire rubber composition according to an embodiment of the present invention can secure Snow/Ice braking performance without deteriorating wet braking performance while securing low-temperature flexibility by adding alkyl phosphate instead of process oil, By applying it as an alternative, it is possible to reduce the oil migration phenomenon, thus minimizing the change in tire performance over time. In another aspect, there is also an effect of preventing deterioration in wet braking performance.

10: tire
100: tread
200: side wall part
300: bead part
400: carcass layer
500: bead core
600: belt layer
700: inner liner
800: cap fly

Claims (11)

Tire rubber composition comprising a C ₁ -C _{60 alkyl phosphate.} The tire rubber composition according to claim 1, wherein _{the alkyl group of the C 1} -C ₆₀ alkyl phosphate is a branched chain. The tire rubber composition of claim 1, wherein the C ₁ -C ₆₀ alkyl phosphate has a structure represented by the following Formula 1:
<Formula 1>

In Formula 1, R ₁ to R ₃ each independently represent hydrogen or a C ₁ -C ₂₀ alkyl group, except when all of _{R 1} to R _{3 are hydrogen.} The method of claim 1,
In Formula 1, R ₁ , R ₂ and R ₃ are all of the same substituent tire rubber composition. The method of claim 1,
Tire rubber composition in which the alkyl phosphate of Formula 1 is the following compound:

The method of claim 1,
Tire rubber composition wherein the rubber composition comprises styrene-butadiene rubber and butadiene rubber as raw rubbers. The tire rubber composition according to claim 6, wherein the styrene-butadiene rubber is 30 to 70 parts by weight based on 100 parts by weight of the raw rubber, and 70 to 30 parts by weight of the butadiene rubber. The method of claim 1,
Tire rubber composition wherein the tire rubber composition contains silica as a filler. The method of claim 1,
The tire rubber composition comprises 1.00 to 20.0 parts by weight of _{the C 1} -C ₆₀ alkyl phosphate based on 100 parts by weight of the raw rubber. The method of claim 1,
Tire rubber composition, wherein the rubber composition is for a tire tread. A tire made of the tire rubber composition of claim 1.

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