KR101370562B1 - The tire sidewall compound - Google Patents

Abstract

The present invention relates to a tire sidewall rubber composition, and more particularly, to a tire sidewall rubber composition comprising 40 to 70 parts by weight of carbon black impregnated with PTFE with respect to 100 parts by weight of raw material rubber. It relates to a tire comprising a tire sidewall rubber composition, a rubber made of the rubber composition, and a rubber made of the rubber composition, which can prevent the tire sidewall from being contaminated from the liquid phase present on the road, thereby suppressing the deterioration of the appearance of the tire. .

Description

Tire sidewall rubber composition

The present invention relates to a tire sidewall rubber composition, and more particularly, to a tire sidewall rubber composition comprising 40 to 70 parts by weight of carbon black impregnated with PTFE with respect to 100 parts by weight of raw material rubber. It relates to a tire comprising a tire sidewall rubber composition, a rubber made of the rubber composition, and a rubber made of the rubber composition, which can prevent the tire sidewalls from being contaminated from the liquid phase present on the road, thereby suppressing the deterioration of the appearance of the tire. .

The exterior of the tire contains most of the information on the tread and tires that move, steer, and support the vehicle through contact with the ground, and contains various patterns, emphasizing external beauty and at the same time It is composed of two parts such as sidewall which reduces the vibration caused by friction and improves the riding comfort.

Among the sidewalls, white rubber or various patterns are used to satisfy some consumer groups. However, the sidewalls are highly polluted in terms of driving and weather conditions. These issues are frustrating for many consumers.

Therefore, much research has been made on techniques for improving the appearance of tire sidewalls and / or suppressing contamination.

Conventional techniques for improving the appearance and / or suppression of tire sidewalls include techniques for improving ozone crack resistance and appearance through plasma treatment on sidewalls. In this case, there is a disadvantage in that a time and cost increase until the tire is released from the secondary process of plasma processing the finished tire, and enormous costs for the addition of equipment are consumed.

There is also a technique to add holographic glitter with metal deposited on the embossed film to the sidewalls, but if the embossed film is not suitable enough to withstand the load that the interaction with carbon or polymer takes on the actual driving, If the dispersion is low, there is a disadvantage that the agglomerated portion can be the starting point of the crack.

In addition, there is a method of improving the type and spec of anti-aging agent used in the tire sidewall rubber composition, but due to the nature of the preservative, when it reacts with ozone in the air, a thin layer is formed on the outside of the sidewall, which may cause discoloration. The only drawback is that

In the present invention, in order to supplement the above-mentioned problems, by adding a carbon-impregnated material (PTFE), which is impregnated in a hydrophobic material, to the tire sidewall portion, the tire comprising the rubber composition as a sidewall is provided. Tire sidewall rubber composition which does not require car processing and can prevent the tire sidewall from being contaminated by the liquid accumulated on the road on rainy or snowy roads, thereby suppressing the deterioration of the appearance of the tire, the rubber composition comprising the rubber composition and the rubber It is intended to provide a tire comprising a rubber made of the composition.

On the other hand, as a patent prior art related to the present invention in Korea Patent Publication No. 2011-0083385 (name of the invention: sidewall rubber composition with improved blooming phenomenon and a tire using the same) to 100 parts by weight of the raw material rubber modified with an alkyl oxide light base Sidewall rubber composition further comprises 5 to 10 parts by weight of the vegetable oil-based softener has the advantage of improving the appearance of the tire by improving the blooming phenomenon without affecting the physical properties of the rubber composition and adhesive properties with other rubber It shows that it has.

In Korean Patent Publication No. 2011-0027100 (name of the invention: tire sidewall rubber composition), a hologram glitter [PET film embossed metal deposited on a film embossed with respect to 100 parts by weight of raw material rubber] Deposition of aluminum after embossing] It is a tire sidewall rubber composition which includes 5 to 20 parts by weight to improve the quality of appearance and has a characteristic of shining in various colors when exposed to sunlight.

However, the patent prior art is different from the present invention because the configuration of the present invention and the technical features of the Dashby invention are different from each other.

The present invention provides a tire sidewall rubber composition, a rubber made of the rubber composition and the rubber composition, which can prevent the tire sidewall from being contaminated from the liquid phase present in rain and / or snow roads, thereby suppressing the deterioration of the appearance of the tire. It is possible to provide a tire comprising a rubber made.

The present invention provides a tire sidewall rubber composition comprising 40 to 70 parts by weight of carbon black impregnated with PTFE (polytetrafluoroethylene) with respect to 100 parts by weight of the rubber material, the rubber composition comprising the rubber composition. And to provide a tire comprising a rubber consisting of the rubber composition.

The present invention provides a tire sidewall rubber composition, a rubber made of the rubber composition and the rubber composition, which can prevent the tire sidewall from being contaminated from the liquid phase present in rain and / or snow roads, thereby suppressing the deterioration of the appearance of the tire. It is possible to provide a tire comprising a rubber made.

This invention shows the tire sidewall rubber composition which can suppress the quality fall of a tire sidewall.

The present invention provides a tire sidewall rubber composition which can prevent the tire sidewalls from being contaminated from the liquid phase present on rain roads and / or snow roads, thereby suppressing the deterioration of the appearance of tires.

The present invention relates to a tire sidewall rubber composition comprising PTFE-impregnated carbon black obtained by impregnating carbon black with PTFE (polytetrafluoroethylene) having hydrophobic properties as an additive to a raw material rubber, and present on roads of rain and / or snow. The tire sidewall rubber composition which can prevent the tire sidewall from being contaminated from the liquid phase and can suppress the deterioration of the appearance of the tire.

The present invention provides a tire sidewall rubber composition comprising 40 to 70 parts by weight of PTFE impregnated carbon black obtained by impregnating carbon black with PTFE (polytetrafluoroethylene) having hydrophobic properties as an additive with respect to 100 parts by weight of raw rubber. And / or a tire sidewall rubber composition which can prevent the tire sidewall from being contaminated from the liquid phase present on snowy roads and can suppress the deterioration of the appearance of the tire.

The carbon black impregnated with PTFE (polytetrafluoroethylene) is added 40 to 90 parts by weight of carbon black to 100 parts by weight of PTFE dispersion solution and stirred at 100 to 500 rpm for 1 to 2 hours to disperse the carbon black. After heating for 1 to 2 hours at 60 to 90 ℃, cooled to 20 to 25 ℃, spread in a sheet (sheet) and dried at 100 to 120 ℃ for 24 to 48 hours to remove moisture of the sheet and then 40 to 200 nm size The ground mill can be used.

PTFE impregnated carbon black (PTFE impregnated carbon black) is added to 85 parts by weight of carbon black relative to 100 parts by weight of PTFE dispersion solution and stirred at 250rpm for 1 hour to disperse the carbon black in PTFE dispersion solution and 1 at 70 ℃ After heating for a period of time and then cooled to 25 ℃ form a sheet (sheet) and dried at 100 ℃ for 24 hours to remove the moisture of the sheet can be used to pulverized to 100 ± 5nm size.

In the production of carbon black impregnated with PTFE, carbon black may have a BET of 80 to 150 m ² / g and a DBP adsorption value of 120 to 200 ml / 100 g.

When the carbon black impregnated with PTFE, the PTFE dispersion solution is selected from SLS (Sodium Lauryl Sulfate) and SDS (Sodium Dodecyl Sulfate) as 40 to 60 parts by weight PTFE and dispersant or dispersion stabilizer based on 100 parts by weight of water. One or more of 5 to 6% by weight of PTFE may be used.

When the carbon black impregnated with PTFE, the PTFE dispersion solution used SLS (Sodium Lauryl Sulfate) and SDS (Sodium Dodecyl Sulfate) alone as 50 parts by weight of PTFE and PTFE as a dispersant or dispersion stabilizer based on 100 parts by weight of water. Or they may be mixed with the same weight ratio that contains 5 to 6% by weight of PTFE.

The sheet of carbon black impregnated with PTFE may have a thickness of 0.1 to 10 mm, and a cross section may be formed in any one shape selected from circles, ellipses, and quadrangles.

In the carbon black manufacturing sheet impregnated with PTFE, the sheet has a thickness of 0.5 mm and a cross section may be formed in any one shape selected from circles, ellipses, and quadrangles.

In the above, the raw rubber may be natural rubber.

In the above, the raw rubber may be synthetic rubber.

The raw rubber may be a mixed rubber in which natural rubber and synthetic rubber are mixed.

The raw material rubber used in the present invention is natural rubber (NR), solution polymerization styrene-butadiene rubber (S-SBR), emulsion polymerization styrene-butadiene rubber (E-SBR), butadiene rubber (BR), modified butadiene rubber, chlorosul Polyethylene rubber, epichlorohydrin rubber, fluorine rubber, silicone rubber, nitrile rubber, hydrogenated nitrile rubber, nitrile butadiene rubber (NBR), modified nitrile butadiene rubber, chlorinated polystyrene rubber, styrene ethylene butylene styrene ( SEBS) rubber, ethylene propylene rubber, ethylene propylene diene (EPDM) rubber, hypalon rubber, chloroprene rubber, ethylene vinyl acetate rubber, acrylic rubber, hydrin rubber, vinyl benzene chloride styrene butadiene rubber, bromomethyl styrene butyl rubber , Styrene butadiene rubber maleic acid, styrene butadiene rubber carboxylic acid, epoxy isoprene rubber, ethylene propylene rubber maleate, nitrile carboxylate Any one or more selected from, butadiene rubber and brominated polyisobutyl isoprene-co-paramethyl styrene (BIMS) may be used.

As the raw material rubber, two or more selected from natural rubber and synthetic rubber may be mixed rubbers in which rubbers are mixed, preferably two or more kinds of rubbers in which four or less rubbers are mixed.

The raw material rubber may be a mixed rubber mixed in a weight ratio of 1 to 9: 9 to 1 when using a mixed rubber of two selected from natural rubber and synthetic rubber.

The raw material rubber may be a mixed rubber mixed in a weight ratio of 1 to 8: 1 to 8: 1 to 8 when using a mixture of three selected from natural rubber and synthetic rubber.

The raw material rubber may be a mixed rubber mixed in a weight ratio of 1-7: 1-7: 1-7: 1-7 when using a mixed rubber of four selected from natural rubber and synthetic rubber.

When the carbon black impregnated with PTFE is less than 40 parts by weight based on 100 parts by weight of raw rubber, the physical properties are lowered, thereby improving the function of alleviating the impact caused by flexion or road surface as a function of tire sidewall, but vulnerable to direct impact. If used in excess of 70 parts by weight, the physical properties of the side wall portion is increased too much, there is a risk that it can not play a role in mitigating the impact caused by flexion or road surface.

PTFE impregnated in the carbon black impregnated with the hydrophobic material PTFE is dispersed in the form of a suspension in 10 parts by weight to 100 parts by weight of water, the PTFE particle size can be used that average 0.04 ~ 0.6㎛.

PTFE used in the present invention is excellent in high temperature stability enough to enable continuous use even at a high temperature of 260 ℃, when the coating has a solid form has the smallest coefficient of friction among all existing solids. It has excellent chemical and electrical barrier properties and is close to zero in its ability to absorb water or similar substances.

The reason why the PTFE dispersion solution is that 40 to 60 parts by weight of PTFE is dispersed with respect to 100 parts by weight of water is effective when the impregnated material is applied to the tire sidewall part when dispersed with 10 parts by weight or less of PTFE relative to 100 parts by weight of water. In case of dispersing more than 60 parts by weight of PTFE with respect to 100 parts by weight of water, the carbon black surface is impregnated excessively and the interaction with rubber becomes small, which may act as a starting point of cracks after molding. It may not be so difficult to apply.

The tire sidewall rubber composition of the present invention may further include a functional component to improve the functionality of the sidewall rubber composition.

The present invention may further comprise a functional component in addition to the carbon black impregnated with PTFE (polytetrafluoroethylene) to improve the functionality of the sidewall rubber composition.

In the functional component may further comprise 0.5 to 3 parts by weight based on 100 parts by weight of the raw material rubber.

In the above, starch can be used as the functional ingredient.

The starch may be any one or more selected from corn starch, potato starch, sweet potato starch, tapioca starch, rice starch or wheat starch, wherein the starch has a surface area of ² to 100 m ² / g, preferably Is 15 to 75 m ² / g, more preferably 30 to 50 m ² / g can be used.

The tire sidewall rubber composition of the present invention is an active agent, an anti-aging agent, a process oil, a vulcanizing agent, a vulcanization accelerator, and the like used in a conventional tire sidewall rubber composition in addition to the above-mentioned raw rubber and carbon black impregnated with PTFE (polytetrafluoroethylene). Various additives can be suitably selected and used in predetermined content as needed. However, these are general components used in the tire sidewall rubber composition and are not essential components of the present invention.

The tire sidewall rubber composition of the present invention was carried out under various conditions, and in order to achieve the object of the present invention, it is preferable to provide a tire sidewall rubber composition under the above-mentioned conditions.

The present invention includes rubber produced by the above-mentioned tire sidewall rubber composition.

The present invention includes a tire containing a rubber produced by the above-mentioned tire sidewall rubber composition.

The present invention includes a tire containing as a sidewall the rubber produced by the above-mentioned tire sidewall rubber composition.

The tire may be any one selected from a tire for a passenger car, a tire for a bus, a tire for a truck, a tire for an aircraft, a tire for a motorcycle or a tire for a tricycle.

Hereinafter, the present invention will be described by the following Preparation Examples, Examples, Comparative Examples and Test Examples. However, the scope of the present invention is not limited by these embodiments.

<Production Example>

Add 85 parts by weight of carbon black to 100 parts by weight of PTFE dispersion solution, stir at 250 rpm for 1 hour to disperse carbon black in PTFE dispersion solution, heat at 70 ° C. for 1 hour, and then cool to 25 ° C. Was formed and dried at 100 ° C. for 24 hours to remove moisture from the sheet, and then ground to a size of 100 ± 5 nm to prepare carbon black impregnated with PTFE.

In the above PTFE dispersion solution, 50 parts by weight of polytetrafluoroethylene (PTFE) and 50 parts by weight of PTFE and sodium lauryl sulfate (SLS) and sodium dodecyl sulfate (SDS) are mixed in a weight ratio of 1: 1 by weight. 6% by weight of PTFE was used.

Carbon black added to the PTFE dispersion solution in the above was used BET of 115 ± 2m ² / g, DBP adsorption of 160 ± 2ml / 100g.

The sheet was formed to have a thickness of 1 mm and a cross section to have a rectangular shape.

&Lt; Example 1 >

40 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example and 3 parts by weight of zinc oxide (ZnO) based on 100 parts by weight of a raw material solid comprising 50 parts by weight of natural rubber, 20 parts by weight of butyl rubber and 30 parts by weight of styrene-butadiene rubber. , 1.5 parts by weight of stearic acid, 3 parts by weight of process oil, and 5 parts by weight of an anti-aging agent (6PPD) were added to a Banbury Mixer and blended to obtain a rubber compound.

2 parts by weight of sulfur as a vulcanizing agent and 1 part by weight of Nt-butylbenzothiazol sulfenamide (NS) as a vulcanizing agent were added to the rubber compound, followed by vulcanization at a temperature of 160 ° C. for 20 minutes. It was.

Rubber composition component ratios of Example 1 are shown in Table 1 below.

<Example 2>

Rubber was manufactured in the same manner as in Example 1, except that 50 parts by weight of carbon black impregnated with PTFE was used instead of 40 parts by weight of carbon black impregnated with PTFE.

Rubber composition component ratio of the said Example 2 is shown in Table 1 below.

&Lt; Example 3 >

Rubber was manufactured in the same manner as in Example 1, except that 60 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example was used instead of 40 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example.

Rubber composition component ratios of Example 3 are shown in Table 1 below.

<Example 4>

Rubber was manufactured in the same manner as in Example 1, except that 70 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example was used instead of 40 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example.

The rubber compositional component ratio of Example 4 is shown in Table 1 below.

<Comparative Example>

Except for 40 parts by weight of carbon black impregnated with PTFE prepared in Preparation Example, except that 40 parts by weight of carbon black having a BET value of 120 ± 5 m ² and a dibutyl phthalate (DBP) adsorption value of 150 ± 5 ml / 100 g was used. Rubber was manufactured in the same manner as in Example 1.

Rubber composition component ratios of the comparative examples are shown in Table 1 below.

Examples and Comparative Examples Rubber composition (unit: parts by weight) division Comparative Example Example 1 Example 2 Example 3 Example 4 Natural rubber 50 50 50 50 50 Butadiene rubber 20 20 20 20 20 Styrene-butadiene rubber 30 30 30 30 30 Antioxidant 5 5 5 5 5 Carbon black * 40 - - - - Zinc oxide (ZnO) 3 3 3 3 3 Stearic Acid 1.5 1.5 1.5 1.5 1.5 Process oil 3 3 3 3 3 Vulcanizing agent 2 2 2 2 2 Vulcanization accelerator One One One One One Hydrophobic Carbon Black ** - 40 50 60 70

Carbon black with BET value of 120 ± 5 m ² and dibutyl phthalate (DBP) adsorption value of 150 ± 5 ml / 100 g

** Carbon black impregnated with PTFE manufactured in the manufacturing example

<Test Example>

Rheometer (Rheometer, @ 160 ℃), Mooney Viscosity (Mooney Viscosity) according to ASTM regulations for the rubber specimens obtained from the rubber prepared in Examples 1 to 4 and the rubber specimens obtained from the rubber prepared in Comparative Example , Tensile properties, the contact angle (Water Resistivity Contact Angle) between the surface of the rubber and the water was measured and their results are shown in Table 2 below.

Examples and Comparative Examples Rubber Properties division Comparative Example Example 1 Example 2 Example 3 Example 4 Rheometer
(160 ℃) Torque (Max) 32.0 31.8 32.4 33.1 34.3 Torque (Min) 15.0 15.5 15.3 15.7 15.6 T40 6.6 6.7 6.5 6.4 6.4 T90 11.0 11.3 11.1 11.0 10.7 End cure 11.5 11.5 11.3 11.2 11.0 Mooney
Viscosity Vistosity
(125 DEG C) 32.0 31.7 33.1 34.1 34.3 T05 33.0 32.6 32.1 31.5 31.1 T35 37.0 38.0 34.2 34.0 33.5 Viscosity
(100 DEG C) 55.0 54.9 56.1 58.0 58.9 Tensile Early
(Ini) Hardness 51.0 51.0 53.0 55.0 56.0 100% -Modulus 16.0 16.2 17.1 17.9 18.6 300% -Modulus 67.0 68.4 68.2 69.7 71.0 Tensile-
Strength 170.0 171.2 173.2 173.9 174.3 Elongation 600.0 599.2 581.3 578.6 571.6 Aging
(Aged) Hardness 55.0 55.0 57.0 58.0 58.0 100% -Modulus 21.0 20.7 22.1 22.9 23.1 300% -Modulus 90.0 88.6 91.3 92.4 92.9 Tensile-
Strength 150.0 152.3 153.4 156.2 158.4 Elongation 470.0 472.6 468.2 457.3 455.1 Water resistivity Contact Angle
(°) 94 105 122 131 135

Aging: The rubber specimens were left at 105 ° C for 24 hours.

As shown in Table 2, the rubber prepared in Examples 1 to 4, including carbon black impregnated with a hydrophobic material of the present invention, has a contact angle between the surface of the rubber and water as compared to the conventional rubber prepared in Comparative Example. It can be seen that the content of carbon black impregnated with PTFE is continuously increased until a certain level is increased, thereby significantly reducing the possibility of contamination by liquids accumulated on rain and / or snow roads.

Therefore, when the rubber made of a sidewall rubber composition containing carbon black impregnated with the hydrophobic material of the present invention is applied to the sidewall of the tire, the sidewall of the tire may be contaminated by a liquid or the like accumulated on the road surface of the tire. The possibility is markedly reduced to provide a tire capable of suppressing the deterioration of the tire appearance quality.

&Lt; Example 5 >

50 parts by weight of carbon black impregnated with PTFE prepared in the preparation example, 3 parts by weight of starch, and zinc oxide (100 parts by weight of raw material consisting of 50 parts by weight of natural rubber, 20 parts by weight of butyl rubber and 30 parts by weight of styrene-butadiene rubber) 3 parts by weight of ZnO), 1.5 parts by weight of stearic acid, 3 parts by weight of process oil, and 5 parts by weight of an antioxidant (6PPD) were added to a Banbury Mixer and blended to obtain a rubber compound.

2 parts by weight of sulfur as a vulcanizing agent and 1 part by weight of Nt-butylbenzothiazol sulfenamide (NS) as a vulcanizing agent were added to the rubber compound, followed by vulcanization at a temperature of 160 ° C. for 20 minutes. It was.

In the starch, corn starch having a BET value of 45 ± 1 m ² / g was used.

<Example 6>

A rubber was prepared in the same manner as in Example 5, except that potato starch having a BET value of 45 ± 1 m ² / g was used instead of corn starch.

&Lt; Example 7 >

Rubber was prepared in the same manner as in Example 5 except for using tapioca starch having a BET value of 45 ± 1 m ² / g instead of corn starch.

As described above, the present invention has been described with reference to preferred embodiments, examples, comparative examples and test examples of the present invention. However, those skilled in the art will appreciate that various modifications, additions and substitutions are possible without departing from the spirit and scope of the present invention It will be understood that various modifications and changes may be made in the present invention.

The present invention provides a tire sidewall rubber composition, a rubber made of the rubber composition and the rubber composition, which can prevent the tire sidewall from being contaminated from the liquid phase present in rain and / or snow roads, thereby suppressing the deterioration of the appearance of the tire. It is possible to provide a tire comprising a rubber made to contribute to the development of the tie and related industries, there is industrial applicability.

Claims (5)

In a tire sidewall rubber composition comprising 40 to 70 parts by weight of carbon black impregnated with PTFE (polytetrafluoroethylene) based on 100 parts by weight of raw material rubber,
The carbon black impregnated with PTFE is added with 40 to 90 parts by weight of carbon black to 100 parts by weight of PTFE dispersion solution, stirred at 100 to 500 rpm for 1 to 2 hours to disperse the carbon black, and 1 to 60 to 90 ° C. After heating for 2 hours and cooling to 20-25 ℃, then spread out in a sheet (sheet) and dried at 100-120 ℃ for 24 to 48 hours to remove the moisture of the sheet, then pulverized to 40-200nm size,
The carbon black has a BET of 80-150 m ² / g and a DBP adsorption value of 120-200 ml / 100 g;
The PTFE dispersion solution is 40 to 60 parts by weight based on 100 parts by weight of water and any one or more selected from SLS (Sodium Lauryl Sulfate) and SDS (Sodium Dodecyl Sulfate) as a dispersant or dispersion stabilizer of PTFE 5-6 by weight % Contained;
The sheet (sheet) has a thickness of 0.1 to 10mm, the cross-section is a tire sidewall rubber composition, characterized in that any one selected from a circle, ellipse, square. delete The method of claim 1,
A tire sidewall rubber composition, further comprising 1 to 10 parts by weight of starch based on 100 parts by weight of raw rubber. A rubber comprising the rubber composition of claim 1. A tire comprising a rubber comprising the rubber composition of claim 1.