KR102023494B1 - Tire Composition for preventing slide - Google Patents

Abstract

The present invention is an acrylic polymer of a core-shell structure having a glass transition temperature of 0 ℃ to -60 ℃; And it relates to a non-slip composition for a tire comprising a solvent, and relates to a composition that improves the braking performance on the snow road or ice by improving the friction and the grip on the road surface by spraying directly on the tire ground surface to coat the surface.

Description

Anti-slip composition for tires {Tire Composition for preventing slide}

The present invention relates to a non-slip composition for a tire, and the composition relates to a composition for improving the braking performance on snowy roads or ice by improving the friction and the grip on the road surface by directly spraying on the tire ground surface and coating the surface.

In order for a vehicle to drive, a friction force must be secured between the road surface and the tire. However, in winter, snow often accumulates on the road or freezes and becomes ice, and the coefficient of friction rapidly decreases between the tire and the road, leading to a large accident if the vehicle slips. This can seriously damage not only the driver but also the town electronics, and in order to prevent car accidents, the government or the road works put a lot of money into winter road management.

In order to increase the driving force and the braking force of the tire, the conventional method employs the principle of increasing the friction between the tire and the snow surface by providing spike pins on the tread surface. However, spike tires are mainly used in extreme areas, and their use is regulated due to growing interest in the environment due to the problem of generating noise on the general road surface and generating dust by causing spikes to damage the road surface.

In addition, the motor vehicle driver may install a snow chain made of metal on a vehicle driving wheel or replace it with a winter tire every winter in order to ensure safe driving in winter. However, this is expensive and time-consuming, especially when the snow chain is installed on the tire, there is a risk of damage to the suspension and bodywork of the car. In addition, replacing tires for winter had a lot of time and expense in that it is necessary to purchase and replace winter tires separately from the existing tires. In addition, there is a conventional spray-type anti-slip agent made by dissolving rosin in toluene, but there is a problem in that the non-slip effect is not long and contains toxic toluene.

The present invention is to solve the problems described above, the object of the present invention is to provide a non-slip agent to ensure a braking force on the road surface easily and quickly in use when unexpected snow during winter driving.

In addition, the present invention provides a non-slip composition that can reduce the damage of the road without affecting the sensor device and the risk of damage to the suspension and the vehicle body of the vehicle, the present invention has a non-slip effect than the conventional spray-type anti-slip agent It has the advantage of excellent sustainability.

The present invention provides a non-slip composition for a tire comprising a core-shell acrylic polymer having a glass transition temperature of 0 to -60 ° C and a solvent. The composition may be provided in a spray type using a propellant.

The present invention can be simply sprayed in preparation for ice and snow running, and by using the acrylic polymer of the core-shell structure, the effect of increasing the traction and friction on the road surface is superior to the conventional anti-slip composition.

The present invention can be easily and quickly used in the tire of the car as a non-slip agent that can replace the existing snow chains, winter tires to secure the necessary friction force during the winter driving, and at the same time the installation cost of winter tires or snow chains And to a non-slip composition which makes it possible to save time.

The present invention is environmentally friendly because it does not contain toxic substances such as toluene, unlike conventional products, and when the present invention is sprayed on a tire, the anti-slip effect and durability are excellent.

In the following, exemplary embodiments according to the present invention will be described. Various modifications, adjustments or variations of the exemplary embodiments described herein may be apparent to those skilled in the art as disclosed. All such changes, adjustments, or modifications that depend on the teachings of the present invention, and the technical field in which the teachings have evolved, should be considered to be within the scope and spirit of the present invention.

The polymers and compositions of the present invention may suitably comprise, consist of, or consist essentially of the components, elements, and process delineation described herein. The inventions described exemplarily herein may be suitably carried out in the absence of any element not specifically disclosed herein.

Unless stated otherwise, all percentages, parts, and ratios expressed herein are based on the weight of the total composition of the present invention.

As used herein, the terms "core-shell", "core-shell form", "core-shell structure", "core-shell portion" are used interchangeably, and each order or step of monomer repeat units is a repeat unit. Refers to a polymer or polymer particle produced by a sequential or staged polymerization process in which the polymerization is completed before the subsequent order or step of polymerisation, these core-shell structured polymers are the core portion and the shell portion physically and / or Chemically bonded and / or attracted to each other.These changes may be somewhat gradual and yield a form having a gradient of polymerizable structure or composition along any radius thereof. Changes in the polymerizable structure or composition can be relatively well defined when moving out from the center along the radius of the particle and include a phase comprising one polymerizable composition. It is possible to produce a shape having a relatively distinct core portion, and a relatively distinct shell portion comprising different polymerizable compositions, The core portion as defined herein can be a polymer which is a linear polymer and one or more shell layers are crosslinked. The rate of change in the polymerizable form of the particle may vary as long as it exerts the necessary properties described herein, wherein the terms "core" and "shell" herein refer to the polymerizable content of the inside and outside of the particle, respectively. (content), and the use of the term should not be construed as meaning that the polymer particles of the present invention necessarily mean a distinct interface between the polymer inside and outside the particles.

It is to be understood that the core-shell polymer particles may be in a form in which the core part is partially coated or encapsulated, as well as in a form in which the core part is fully coated or encapsulated. Further, in describing the "core portion" and "shell portion" of the core-shell portion or core-shell acrylic polymer of the present invention, there will be a substantial amount of interpenetration of the polymer present in the core and shell of the polymer particles. It should be understood that there may be an interpenetration. Thus, the "core part" may expand to the inside of the shell of the particles, forming a region within the shell particles to some extent, and vice versa.

Similar terms, such as the terms "core portion" and "shell portion or" core polymer "and" shell polymer ", are intended to attempt to identify any particular polymer as strictly" shell "or strictly as" core "polymer. It is used herein to describe the polymerizable material in a general manner in the named part of the polymerizable particles.

As used herein, the term “(meth) acrylic” acid is meant to include both acrylic acid and methacrylic acid. Similarly, as used herein, the term "alkyl (meth) acrylate" is meant to include alkyl acrylates and alkyl methacrylates.

The present invention is an anti-slip composition for tires comprising an acrylic polymer and a solvent having a core-shell structure having a glass transition temperature of 0 ° C to -60 ° C. The core-shell structured acrylic polymer refers to an acrylic-based core-shell polymer as core-shell polymer particles.

The acrylic polymer of the core-shell structure of the present invention has a weight average molecular weight of 50,000 to 1,000,000, preferably a weight average molecular weight of 100,000 to 500,000.

In one embodiment of the present invention, preferably, the core portion is a polymer (A) having excellent grip on snowy roads or ice roads, and the shell portion is made of a polymer (B) having excellent adhesion to tires.

In one embodiment of the invention, about 5% to 95% by weight of the acrylic base core polymer (A) and about 95% to 5% by weight of the acrylic substrate based on the total weight of the acrylic polymer of the core-shell structure Crosslinked shell polymer (B). In another aspect, the core-shell structured acrylic polymer comprises from about 20% to about 80% by weight of the acrylic base core polymer (A) and about 80% by weight, based on the total weight of the core-shell structured acrylic polymer. To 20% by weight acrylic based crosslinked shell polymer (B). In yet another aspect, the core-shell structured acrylic polymer may comprise from about 60% to about 40% by weight acrylic base core portion and from about 40% to about 60 based on the total weight of the core-shell structured acrylic polymer. It may comprise a weight percent acrylic based crosslinked shell portion.

<Core part polymer (A) in core-shell structure acrylic polymer>

The core polymer (A) in the core-shell structured acrylic polymer of the present invention is an acrylic base polymer which is polymerized in the absence of a crosslinking monomer, and is applied to tires to provide high visibility and excellent adhesion to a road surface. It is a polymer that has an anti-slip effect by improving against an object). When the core-shell structured acrylic polymer of the present invention is applied to the tire ground surface so that the tire passes over the road surface, the core polymer (A) is exposed by the shell polymer (B) and at the same time the tire is removed from the road surface with excellent grip on the road surface. Prevent slipping.

The core portion polymer (A) is methyl (meth) acrylate, ethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n -Butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Stearyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, tetradecyl (meth) methacrylate, diethylaminoethyl (meth) acrylate and diisopropylaminoethyl ( Meth) acrylate, butyl acrylate, ethyl acrylate, n-butyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth ) Acrylate, (meth) Krylic acid, stearyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, styrene, dihydrodicyclopentadienyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl (Meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, t-butylaminoethyl methacrylate, N, N-Diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, Polymerized with one or more monomers such as 1,3-butanediol dimethacrylate monomers, preferably with butyl acrylate (n-BA) and methacrylate, __ and the like.

The glass transition temperature of the core portion polymer (A) is 0 ° C to -60 ° C, preferably 0 ° C to -20 ° C, and has a high friction characteristics by maintaining a high grip force to the tire even at subzero temperatures Provided is a method for producing a slip resistant rubber material.

<Shell part polymer (B) in core-shell structure acrylic polymer>

The shell polymer (B) in the core-shell structured acrylic polymer particles of the present invention is an acrylic base polymer (B) which is polymerized in the absence of a crosslinking monomer, and has excellent adhesion to tires when the composition of the present invention is applied to a tire. To do that. Accordingly, when the core-shell structured acrylic polymer-containing composition is sprayed onto the tire, the tire has a good adhesion, thereby improving the friction between the tire and the road surface, thereby preventing slippage. The glass transition temperature of the shell polymer (B) is 0 ° C. to -60 ° C., preferably -20 ° C. to -60 ° C., and has a high friction property by maintaining a high grip force on the tire even at subzero temperatures. Provided is a method for producing a rubber material for prevention.

As monomers of the shell polymer (B) in the core-shell structured acrylic polymer, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 3-methoxyethyl (meth) acrylate, and propyl (meth) acrylate , Isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acryl Late, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-phenylethyl (meth) acrylate, benzyl (meth) acrylate, tetradecyl (meth) methacrylate, diethylaminoethyl (meth Acrylate and diisopropylaminoethyl (meth) acrylate, butyl acrylate, ethyl acrylate, n-butyl methacrylate, methyl methacrylate, 2-ethylhexyl acrylate, N, N-dimethylaminoethyl ( Meth) acrylate , Glycidyl (meth) acrylate, (meth) acrylic acid, stearyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, styrene, dihydrodicyclopentadienyl acrylate , Cyclohexyl methacrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, t-butylaminoethyl methacrylate, N, N-Diethylaminoethyl methacrylate , N, N-dimethylaminoethyl methacrylate, 1,3-butanediol dimethacrylate monomer and the like can be used.

In the polymerization of the core portion polymer (A) and the shell portion polymer (B), as the polymerization initiator, those which can be used for ordinary emulsion polymerization can be used, and examples thereof include inorganic peroxides such as potassium persulfate, sodium persulfate and ammonium persulfate, Azo initiators such as organic peroxides, azo-bis-dimethylvaleronitrile, azo-bis-iso-butylnitrile, hydrogen peroxide and benzoyl peroxide, di-t-butyl peroxide, cumene hydroperoxide, t-butylhydroper Oxide, t-butylperoxyoctanoate, t-butylbenzoate, t-butyl peroxyacetate, 3,5,5-trimethylhexanoyl peroxide, diisopropyl peroxy dicarbonate, t-butyl peroxy Redox polymerization initiators such as peroxides such as maleic acid, t-butyl peroxy 2-ethylhexanoate and butyl peroxide, and combinations thereof with reducing agents such as acidic sodium sulfite and L-ascorbic acid; Can be. These can be used individually or in combination of 2 or more types.

Examples of the chain transfer agent include alcohols such as methanol, ethanol, propanol and butanol, aldehydes such as acetaldehyde, propionaldehyde, n-butylaldehyde, furfural and benzaldehyde and dodecylmercaptan, lauryl mercaptan, and normalmer. Mercaptans, such as a captan, thioglycolic acid, octyl thioglycolate, and thioglycerol, etc. are mentioned. These can be used individually or in combination of 2 or more types. The use of a chain transfer agent is effective at the point of making superposition | polymerization stably, and it is preferable to use in order to adjust the polymerization degree of a polymer (A).

In one embodiment of the present invention, the weight ratio of the core polymer (A) and the shell polymer (B) is preferably 1/5 ~ 5/1. If the above range is satisfied, the tire has an excellent adhesion and has an advantage of improving the coefficient of friction during braking on the road surface. In particular, even when snow is accumulated on the road surface or frozen and frozen, the friction coefficient of the tire surface may be improved to maintain a constant frictional force for a long time at low temperature, thereby preventing slipping and reducing the risk of an accident.

In one embodiment of the present invention, the solvent contained in the composition may be any one or more selected from acetate esters, C1 to C4 alcohol, toluene, xylene, xylene, hexane, heptane, in particular using an acetate ester solvent Preferably, propyl acetate or butyl acetate can be used as an example.

In particular, in the present invention, when the acrylic polymer of the core-shell structure having a glass transition temperature of 0 to -60 ° C. is mixed with a solvent of acetic acid esters such as propyl acetate or butyl acetate, eye-braking performance and acceleration performance are very high. Improved compositions can be provided. In one embodiment, the composition of the present invention comprises 1 to 20% by weight of the acrylic polymer of the core-shell structure relative to the total weight; And the solvent includes 30 to 60% by weight.

In addition, the composition of the present invention may additionally include additives commonly used, and may further include a propellant to be used in a spray form. As the propellant, any one or more selected from butane, propane, dimethyl ether, and carbon dioxide may be used. Spray type compositions can be used by simply spraying on the tire surface, unlike snow chains to use, as well as maintaining good friction on snow and ice for a long time.

Example

Preparation Example 1 Preparation of Acrylic Polymer-Containing Composition of Core-Shell Structure

First, a polymer corresponding to the core portion was formed by the following method.

The n-propyl acetate was charged to a kettle, and then heated to 60 ° C. under a nitrogen atmosphere. While maintaining the kettle at 60 ~ 90 ℃, add and mix the acrylate monomers (butyl acrylate, (meth) acrylic acid, methacrylate and ethyl acrylate) with n-propyl acetate in a 1: 1 molar ratio, An initiator and a chain transfer agent (CTA) were added in an amount of 0.01 to 3.0% based on the total weight of the acrylate monomer to bulk polymerize the reaction, and the reaction was continued for 3 hours at a temperature of 60 to 90 ° C. Prepared.

The synthesized polymer was charged in n-propyl acetate and kettle, and then heated to 60 ° C. under a nitrogen atmosphere. While maintaining the kettle at 60 ~ 90 ℃, the acrylate monomers (butyl acrylate, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, methacrylate of Table 1) , 2-ethylhexyl acrylate, n-butyl methacrylate, 2-hydroxyethyl acrylate, styrene monomer, glycidyl (meth) acrylate, stearyl (meth) acrylate, N, N-Diethyl Amino ethyl methacrylate), an initiator and a chain transfer agent were added dropwise for 3 hours, and the reaction was held for an additional 1 hour to form a shell portion such that the weight ratio of the shell portion to the synthesized core portion was 1:10.

The synthesized core-shell structured acrylic polymer and solvent were mixed, and then propane, butane, and dimethyl ether were mixed as propellants to prepare an anti-slip agent.

Preparation Example 2 Preparation of Acrylic Polymer-Containing Composition of Core-Shell Structure

Synthesis was carried out in the same manner as in Preparation Example 1, except that only the components and their contents as shown in Table 1 to prepare a composition of Preparation Example 2.

Comparative Production Example 1

In Comparative Preparation Example 1, a conventional rosin-containing composition was prepared.

Comparative Production Example 2

As Comparative Preparation Example 2, a core portion polymer was synthesized in the same manner as in Preparation Example 1 using the monomers shown in Table 1 below, but the shell portion was not synthesized. An acrylic compound prepared therefrom was mixed with a solvent and a propellant to prepare a non-slip composition by mixing propane, and the glass transition temperature of the acrylic polymer synthesized in this Preparation Example was found to be 10.2 ° C. or more.

Ingredient / Content (% by weight) Content (% by weight) Preparation Example 1 Preparation Example 2 Comparative Production Example 1 Comparative Production Example 2 Core part manufacturing Acrylate Monomer * 2.1 1.8 - 8.5 Chain transfer agent (CTA) 0.0002 0.0002 - 0.0006 Initiator 0.01 0.01 - 0.01 n-propyl acetate 2.1 2.1 - - Shell
Produce Acrylate Monomer * 6.4 5.5 - - - CTA 0.0006 0.0006 - - Azo initiator 0.01 0.01 - - rosin - - 25.0 - solvent n-propyl acetate Balance Balance - Balance toluene - - 38.0 - Propellant Butane, propane, dimethyl ether 40.4 40.4 37.0 40.4

1) Core acrylate monomers of Preparation Examples 1 and 2: butyl acrylate, (meth) acrylic acid, methacrylate, ethyl acrylate

2) Shell part acrylate monomers of Production Examples 1 and 2: butyl acrylate, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, methacrylate, 2-ethylhexyl Acrylate, n-butyl methacrylate, 2-hydroxyethyl acrylate, styrene monomer, glycidyl (meth) acrylate, stearyl (meth) acrylate, N, N-Diethylaminoethyl methacrylate

3) Core part acrylate-type monomer of the comparative manufacture example 2: butyl acrylate, methyl methacrylate, 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, methacrylate, ethyl acrylate , 2-ethylhexyl acrylate, n-butyl methacrylate, styrene monomer, glycidyl (meth) acrylate

Experimental Example:

Example 1: After spraying the composition obtained from Preparation Example 1 evenly on the test tire, the eye-braking performance and eye-acceleration performance was evaluated for the composition.

Example 2: After spraying the composition obtained from Preparation Example 2 evenly on the test tire, the eye-braking performance and eye-acceleration performance was evaluated for the composition.

Comparative Example 1: After spraying the composition obtained from Comparative Preparation Example 1 evenly on the test tire, the eyeball braking performance and the eyeball acceleration performance were evaluated for the composition.

Comparative Example 2: After spraying the composition obtained from Comparative Preparation Example 2 evenly on the test tire, the eyeball braking performance and the eyeball acceleration performance were evaluated for the composition.

<Brake performance evaluation method>

The braking performance test on snow road was repeated 10 times of braking distance until the vehicle was completely stopped by full braking at a speed of 30km / hr under road conditions under Medium Hard Pack (Penetrometer 84-93) air temperature -5 ℃. The average braking distance value was obtained. Road condition measurements were confirmed according to SAE J1466. Specific evaluation methods are as follows.

1) Measure the average braking distance (RD _m ) of the reference tire ( R ). The reference tire is a tire to which no material is applied to improve braking performance, and an average braking distance RD _m is obtained by the following formula.

RD _m = (RD ₁ + RD ₂ + RD ₃ + RD ₄ + RD ₅ + RD ₆ + RD ₇ + RD ₈ + RD ₉ + RD ₁₀ ) / 10

** RD ₁ to RD ₁₀ is the distance measured from 1 to 10 times when the vehicle with reference tire ( R ) is applied at 30km / hr and stopped from the point where T (time) = 0 is applied by sudden braking. to be.

2) Measure the average braking distance of the test tire (Candidate tire, T ) of the Examples and Comparative Examples in the same manner as above.

TD _{m =} (TD ₁ + TD ₂ + TD ₃ + TD ₄ + TD ₅ + TD ₆ + TD ₇ + TD ₈ + TD ₉ + TD ₁₀ ) / 10

** TD ₁ to TD ₁₀ is a distance measured from 1 to 10 times when the vehicle to which the test tire ( T ) is applied is 30 km / hr and stops suddenly and stops from T = 0. .

3) From the obtained RD _m and TD _m values, the brake index (Grip Index, G ) was obtained according to the following equation.

G = TD _m / RD  _m × 100

The higher the braking index, the better the braking performance. A braking index of 100 or more means better braking performance than the reference tire, and a lower braking index means lower braking performance.

Only the vehicle speed was changed to 20 km / hr in the experiment method in the above snow road, and the experiment was performed on the ice road in the same manner, and the results are shown in Table 2.

<Acceleration performance evaluation method>

Acceleration performance tests on snow roads were carried out on a flat Ice-Dry road surface at ambient temperatures below -5 ° C and road surface measurements were confirmed according to SAE J1466. Specific evaluation methods are as follows.

1) After the test vehicle was stopped for a certain time, the average value was obtained by repeating the test 10 times to reach the speed of 30 km / hr from the stationary state.

A reference Thai (Reference tire, R) average acceleration time (RS _m) are measured. The reference tire is a tire to which no material is applied to improve braking performance, and an average acceleration time RS _m is obtained by the following formula.

RS _m = (RS ₁ + RS ₂ + RS ₃ + RS ₄ + RS ₅ + RS ₆ + RS ₇ + RS ₈ + RS ₉ + RS ₁₀ ) / 10

** RS ₁ to RS ₁₀ is a value measured from 1 to 10 times for a vehicle to which a reference tire is applied to reach a speed of 30 km / hr from a stationary state.

2) Measure the average acceleration time of the test tire (Candidate tire, T). The test target tire is a tire of each example and a comparative example.

TS _{m =} (TS ₁ + TS ₂ + TS ₃ + TS ₄ + TS ₅ + TS ₆ + TS ₇ + TS ₈ + TS ₉ + TS ₁₀ ) / 10

** TS ₁ to TS ₁₀ refers to a value measured from 1 to 10 times for the vehicle to which the test tire is applied to reach a speed of 30 km / hr from a stationary state.

3) An Acceleration Index ( A ) was obtained from the obtained RS _m and TS _m values according to the following formula.

A = TSm / RS m × 100

The higher the acceleration index, the higher the acceleration performance. An acceleration index of 100 or more means better acceleration performance on snow than a reference tire, and a lower acceleration index means lower acceleration performance.

Only the vehicle speed was changed to 20 km / hr in the experiment method in the above snow road, and the experiment was performed on the ice road in the same manner, and the results are shown in Table 2.

<Glass Transition Temperature (Tg) Measurement>

Preparation Examples 1 and 2 and Comparative The glass transition temperature (Tg) for the compositions of Preparation Examples 1 and 2 was measured by drying the sample into a film state and heating at a rate of 10 ° C./min using a differential scanning calorimeter.

The results of this experimental example are described in Table 2.

Item Example 1 Example 2 Comparative Example 1 Comparative Example 2 Polymer glass transition temperature (Tg) -19.4 ℃ -20.1 ℃ 75 ℃ 10.2 ℃ Snow Brake Performance (G) 164.6 151.0 126 131 Eye acceleration performance (A) 156.2 145.8 122.3 125.8 Ice Braking Performance (G) 130.7 122.1 109.4 117.8 Ice acceleration performance (A) 125.3 118.6 103.1 105.6

The acrylic polymer in the compositions of Examples 1 and 2 had a glass transition temperature (Tg) of 0 ° C. to about −60 ° C. and had a core-shell structure.

On the other hand, in Comparative Example 1, the composition containing the rosin compound was tested. In Comparative Example 2, the tire was applied to the composition containing the acrylic polymer having no core-shell structure. Comparative Examples 1 and 2 have superior performance compared to the reference tire, but it can be seen that the snow and ice braking / acceleration performance is significantly lower than that of Examples 1 and 2. In particular, Example 1 improved the braking and acceleration performance which was further excellent by mix | blending the acetate-type solvent with the acrylic polymer of a core-shell structure.

Durability performance evaluation

Experimental tires to which the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied were run at 0, 10, 20, 30, and 40 km per hour at 80 km on dry asphalt, and the braking performance was evaluated in snow. The braking performance test on the snow road was carried out by repeating the braking distance 10 times until the vehicle stopped completely by braking the vehicle at a speed of 30 km / hr under Medium Hard Pack (Penetrometer 84-93) road conditions. . Road condition measurements are verified in accordance with SAE J1466. The specific experimental method is the same as described above.

distance driven Example 1 Example 2 Comparative Example 1 Comparative Example 2 Snow braking performance after 0km (G) 155.0 146.6 132.1 138.5 10km after snow braking performance (G) 152.6 142.2 115.3 116.7 Snow Brake Performance after 20km (G) 140.6 137.0 109.5 110.3 30km after snow braking performance (G) 126.5 120.7 103.1 104.2 40km after snow braking performance (G) 123.4 115.8 103.9 102.5

As can be seen from the results in Table 3, the braking characteristics of Examples 1 and 2 including the acrylic polymer of the core-shell structure having a glass transition temperature (Tg) of 0 ° C to about -60 ° C are comparative examples 1 and 2 It can be seen that it is significantly superior to. In particular, in the case of Examples 1 and 2, despite the mileage of 0 to 40 km, the effect of maintaining the frictional force and the grounding force on the road surface is considerable, and it can be seen that the durability of the composition is excellent.

Although the preferred embodiments of the present invention has been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (11)

Core-shell structured acrylic polymer; In the anti-slip composition for tire comprising a solvent,
The core part of the acrylic polymer of the core-shell structure includes a polymer (A) having a glass transition temperature of 0 ° C to -20 ° C.
The shell portion of the acrylic polymer of the core-shell structure comprises a polymer (B) having a glass transition temperature of -20 ° C to -60 ° C, anti-slip composition for a tire. The method of claim 1,
The anti-slip composition for a tire having a weight average molecular weight of 50,000 to 1,000,000 of the acrylic polymer of the core-shell structure. delete The method of claim 1,
The core portion of the core-shell acrylic polymer includes a polymer (A) made of at least one monomer selected from the group consisting of butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and (meth) acrylic acid,
The shell portion of the acrylic polymer of the core-shell structure is lauryl (meth) acrylate, n-butyl methacrylate, stearyl (meth) acrylate, 2-ethylhexyl acrylate, (meth) acrylate methyl methacrylate, Styrene, dihydrodicyclopentadienyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, vinyl acetate, t-butylaminoethyl methacrylate, Polymer (B) made of at least one monomer selected from the group consisting of N, N-Diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate and 1,3-butanediol dimethacrylate Anti-slip composition for tires to be. delete The method of claim 1,
The anti-slip composition for tires whose weight ratio of the said polymer (A) and polymer (B) is 1/5-5/1. The method of claim 1,
The anti-slip composition for tires, wherein the solvent comprises any one or more selected from acetic acid esters, C1 to C4 alcohol, toluene, xylene, xylene, hexane, heptane. The method of claim 1,
An anti-slip composition for a tire wherein the solvent is n-propyl acetate or isopropyl acetate. The method according to any one of claims 1, 2, 4 and 6 to 8,
About the total weight of the composition
The core-shell structure of the acrylic polymer is 1 to 20% by weight; And
The anti-slip composition for a tire comprising the solvent in 30 to 60% by weight. The method of claim 9,
An anti-slip composition for a tire further comprising a propellant. The method of claim 10,
The propellant is an anti-slip composition comprising any one or more selected from butane, propane, dimethyl ether and carbon dioxide.