KR20230037811A - A rubber composition for shoe outsole with excellent abrasion resistance and slip resistance - Google Patents

Abstract

The present invention relates to a rubber composition for a shoe outsole having excellent abrasion resistance and slip resistance. More specifically, the rubber composition according to the present invention comprises: 60 to 90 parts by weight of a silica affinity modified butadiene rubber (BR); 10 to 40 parts by weight of a silica affinity modified solution styrene butadiene rubber (S-SBR); 40 to 70 parts by weight of a filler including silica; and 1 to 8 parts by weight of at least one kind of carbon nanomaterial selected from the group consisting of carbon nanotubes, graphite, and graphene, based on 100 parts by weight of a total high-inorganic material, wherein the carbon nanomaterial is present in a set master batch while being pre-mixed with the silica affinity modified butadiene rubber, the silica affinity modified solution styrene butadiene rubber, or a mixed rubber thereof. According to the present invention, excellent abrasion resistance and slip resistance may be exhibited under various temperature conditions and various road surface conditions.

Description

A rubber composition for shoe outsole with excellent abrasion resistance and slip resistance}

The present invention relates to a rubber composition for a shoe outsole, which is excellent in abrasion resistance and slip resistance even under various temperature conditions and various road surface conditions.

Since shoes are composed of various parts, the main performance of each part is different for each part. Outsole, one of the various parts of shoes, is a part that directly touches the road surface, and has adequate flexibility and appropriate slip resistance (hereinafter referred to as 'slip resistance') to transmit power for walking and maintain stable walking. should have In addition, the outsole of the shoe preferably has excellent abrasion resistance. This is because when the abrasion resistance is excellent, the lifespan of the shoe is extended and the thickness of the shoe can be reduced, so that the weight of the shoe can be reduced.

Various studies and attempts are being made to achieve the above-mentioned object.

1. Republic of Korea Patent Registration No. 10-1662007 (2016.10.04.) entitled 'High wear-resistant rubber composition for shoe outsole and manufacturing method thereof', rubber base material 100 parts by weight, polytetrafluoroethylene powder 0.1 to 50 parts by weight, 5 to 80 parts by weight of a filler and other materials. Here, polytetrafluoroethylene powder can improve wear resistance under special conditions because it is technically difficult to actively crosslink with rubber, but there is a limit to improving wear resistance under various conditions.

2. Republic of Korea Patent Registration No. 10-2000137 (2019.07.16) entitled 'Non-slip outsole rubber base composition' is a rubber base material 100 composed of 40 to 60 parts by weight of butadiene rubber and 40 to 60 parts by weight of natural rubber A rubber composition comprising 10 to 30 parts by weight of non-slip agent waste glass nanotube powder is disclosed. Here, the concept of waste glass nanotubes is ambiguous, and it is practically difficult to commercialize waste glass nanotubes. In addition, it is technically very difficult to nanonize waste glass, but since waste glass has little surface affinity with rubber, there is a disadvantage in that abrasion resistance is remarkably reduced when waste glass of a certain size or more protrudes without nanonization.

3. Republic of Korea Patent Registration No. 10-2092723 (2020.03.24.), entitled 'Rubber composition for shoe outsole with excellent wear resistance and slip resistance', contains 100 parts by weight of rubber base material and 40 to 100 silica masterbatch The silica masterbatch discloses a rubber composition obtained by mixing 100 to 120 parts by weight of silica with respect to 100 parts by weight of a substrate composed of 50 to 70% by weight of liquid NBR and 30 to 50% by weight of powdered NBR. Here, nitrile butadiene rubber (NBR), which has a relatively higher affinity for silica than butadiene rubber, is included. Depending on the content of acrylonitrile, the glass transition temperature can be greatly increased, and flexibility at low temperatures is rapidly reduced, resulting in low temperature There is a disadvantage that the slip resistance in is lowered (existence of temperature sensitivity).

In general, a reinforcing agent having small particles and a developed structure may be used to improve wear resistance. However, since reinforcing agents having small particles and well-developed structures are not easily dispersed, it is difficult to improve wear resistance. In addition, the reinforcing agent having excellent compatibility with the rubber material can improve the abrasion resistance in relation to the dispersibility of the compounded rubber. In addition, a raw material rubber having relatively excellent wear resistance may be selected and used, and thus the wear resistance may be improved to some extent. However, slip resistance may deteriorate. Conversely, if the slip resistance is improved, the abrasion resistance may be lowered. In particular, in order to improve slip resistance on wet road surfaces, rubber material researchers/designers can use silica. Although slip resistance can be improved, wear resistance is rather deteriorated due to its low affinity with general rubber. Because of this antinomian performance, it can be said that it is a technically very difficult task to simultaneously improve wear resistance and slip resistance.

Republic of Korea Patent Registration No. 10-1662007 (2016.10.04.) Republic of Korea Patent Registration No. 10-2000137 (2019.07.16.) Republic of Korea Patent Registration No. 10-2092723 (2020.03.24.)

An object of the present invention is to design a shoe outsole that exhibits excellent abrasion resistance and slip resistance even under various temperature conditions and various road surface conditions.

The present invention relates to a rubber composition for shoe outsole with excellent abrasion resistance and slip resistance, and 60 to 90 parts by weight of specially selected silica affinity-modified butadiene rubber (BR) based on 100 parts by weight of the total rubber base material, specially selected silica affinity modification Solution 10 to 40 parts by weight of styrene butadiene rubber (S-SBR), 40 to 70 parts by weight of a filler containing silica, and at least one carbon nanomaterial selected from the group consisting of carbon nanotubes, graphite and graphene 1 to 8 The carbon nanomaterial is pre-mixed with silica affinity-modified butadiene rubber or silica affinity-modified solution styrene butadiene rubber or a mixture rubber thereof and used as a wet master batch.

Preferably, the silica affinity-modified butadiene rubber is NDBR (Neodymium-Butadiene Rubber) having a sheath content of 95% by weight or more and a weight average molecular weight distribution (MWD) of 2.1 to 3.1, and the silica affinity-modified solution styrene butadiene The rubber is characterized by a styrene unit content of 15 to 30% by weight, a vinyl unit content of 30% by weight or more, a glass transition temperature of less than -50.0 ° C, and a weight average molecular weight distribution (MWD) of 1.3 to 3.0.

The present invention can provide a shoe outsole exhibiting excellent abrasion resistance and slip resistance even under various temperature conditions and various road surface conditions.

Hereinafter, the present invention will be described in detail. However, the present invention is not limited or limited by exemplary embodiments. The objects and effects of the present invention can be naturally understood or more clearly understood by the following description, and the objects and effects of the present invention are not limited only by the following description. In addition, in describing the present invention, if it is determined that a detailed description of a known technology related to the present invention may unnecessarily obscure the subject matter of the present invention, the detailed description will be omitted.

The present invention relates to a rubber composition for shoe outsoles with excellent abrasion resistance and slip resistance, and based on 100 parts by weight of the total rubber base material, 60 to 90 parts by weight of silica affinity modified butadiene rubber (BR), silica affinity modified solution styrene 10 to 40 parts by weight of butadiene rubber (S-SBR), 40 to 70 parts by weight of a filler containing silica, and 1 to 8 parts by weight of at least one carbon nanomaterial selected from the group consisting of carbon nanotubes, graphite and graphene The carbon nanomaterial is pre-mixed with silica affinity-modified butadiene rubber, silica affinity-modified solution styrene butadiene rubber, or a mixture rubber thereof and exists as a wet master batch.

The rubber composition according to the present invention is generally similar to that used as a compounding agent for shoes and may include 0.5 to 3.0 parts by weight and 0.5 to 5.0 parts by weight of a vulcanizing agent and a vulcanization accelerator, respectively, and anti-aging agents, processing aids, etc. are conventional content can be used. The rubber composition according to the present invention is significant in that it solves all of the problems 1) to 4).

1) In general, the property of rubber materials in rubber products is viscoelasticity. Accordingly, when the property of elasticity is increased, the property of viscosity is relatively lowered, and the slip resistance is lowered. Conversely, if the viscosity property is increased to improve slip resistance, wear resistance and mechanical strength are lowered. In addition, these properties change depending on the material and temperature.

2) Since the slip resistance is greatly reduced on a wet or frozen road surface, a hydrophilic material such as silica can be used to reinforce it. However, since silica has low affinity with rubber, a substance that promotes dispersion of silica and induces a reaction between silica and rubber is added, but the problem of deterioration in slip resistance is not completely overcome.

3) In the field of tires, raw material rubber and silica are actively researched and developed to overcome the problem of deterioration in slip resistance. It is impossible to apply it directly to the field.

4) In the case of nanomaterials currently being researched and developed, even if the performance of nanomaterials is excellent, it is practically very difficult to effectively disperse in rubber and exhibit its performance in its entirety. skill is required

Hereinafter, the specific configuration of the rubber composition according to the present invention will be described.

1. Butadiene rubber

Butadiene rubber, in general, has a relatively low glass transition temperature and thus has a small performance change under daily temperature conditions and a relatively high abrasion resistance. However, butadiene rubber has relatively low slip resistance (grip property) as much as it has high elasticity. For this reason, butadiene rubber is preferably used in combination with styrene butadiene rubber as appropriate in order to supplement low slip resistance. In particular, it is preferable to additionally use silica to improve slip resistance on wet or frozen road surfaces.

However, general synthetic rubber is easily mixed and bonded with lipophilic materials such as carbon black and exhibits excellent wear resistance and mechanical properties, whereas silica is a hydrophilic material, so mixing and bonding with general synthetic rubber is very difficult. To solve this problem, when using silica, a silane coupling agent that binds silica and rubber may be used. However, since there is a limit to the bond between silica and rubber, it is preferable to use a silica affinity-modified butadiene rubber having modified rubber chains or terminals capable of direct physical and chemical bonding between silica and rubber. Through this, it is possible to simultaneously improve abrasion resistance and slip resistance of rubber for shoe outsoles.

The rubber composition for a shoe outsole according to the present invention preferably includes 60 to 90 parts by weight of silica-affinity modified butadiene rubber. More preferably, High-Cis modified butadiene rubber having a Cis content of 95% by weight or more may be used. The functional group used for modification consists of a polyorganosiloxane group, a polyorganosiloxane group containing a hydroxyl group, an alkoxy silyl group, a hydroxyl group, an aldehyde group, a carboxyl group, an amino group, an imino group, an epoxy group, an amide group, a thiol group, and an ether group. It may be at least one functional group selected from the group. Any functional group can be used as long as it has reactivity with a silanol group on the silica surface, and is not limited to the above-mentioned functional group, but among these, a polyorganosiloxane group is more preferable.

2. Styrene butadiene rubber

Silica affinity modified solution Styrene butadiene rubber is used to balance the simultaneous improvement of abrasion resistance and slip resistance. When the content of the above-mentioned butadiene rubber is high, the abrasion resistance is improved but the slip resistance is lowered, and when the content of styrene butadiene rubber is high, the opposite is true. The rubber composition for shoe outsole according to the present invention preferably contains 10 to 40 parts by weight of silica affinity-modified solution styrene butadiene rubber. Since styrene butadiene rubber is also lipophilic like the above-mentioned butadiene rubber, its performance can be improved by giving silica affinity for mixing and bonding with silica.

In styrene-butadiene rubber, when the styrene content is high, the slip resistance is improved, but the abrasion resistance is lowered, and the glass transition temperature is increased, so that the rubber properties tend to rapidly deteriorate at low temperatures. For this reason, it is preferable to use a styrene-butadiene rubber having a styrene unit content of 15 to 30% by weight and a vinyl unit content of 30% by weight or more. In order to control the contents of styrene and vinyl, it is preferable to use a solution styrene butadiene rubber manufactured by a solution method. When the glass transition temperature is high, it is preferable to use a material having a glass transition temperature of less than -50.0 ° C.

In addition, as described above, in order to use silica, it is preferable to use silica affinity modified solution polymerized styrene butadiene rubber, and the functional group used for modification is a polyorganosiloxane group, a hydroxyl group-containing polyorganosiloxane group , It may be at least one functional group selected from the group consisting of an alkoxysilyl group, a hydroxyl group, an aldehyde group, a carboxyl group, an amino group, an imino group, an epoxy group, an amide group, a thiol group, and an ether group. Any functional group can be used as long as it can have reactivity with a silanol group on the silica surface, and is not limited to the above-mentioned functional groups, but among them, a hydroxyl group-containing polyorganosiloxane group, an alkoxy silyl group, a hydroxyl group, an aldehyde group, a carboxyl group , an amino group and an epoxy group are more preferable.

3. Carbon nano materials

The rubber composition for a shoe outsole according to the present invention may include at least one carbon nanomaterial selected from the group consisting of carbon nanotubes, graphite, and graphene. Carbon nanomaterials can be used to improve mechanical strength and wear resistance. When using the above-described carbon nanomaterial, it may not be dispersed so that the performance of the carbon nanomaterial is sufficiently expressed only by general mixing.

For effective dispersion and processing, it is preferable to use a wet master batch in which a rubber substrate is impregnated with a carbon nanomaterial. As the rubber base material, the above-described silica affinity-modified butadiene rubber, silica affinity-modified solution styrene butadiene rubber, or a mixture rubber thereof, that is, a mixture of silica affinity-modified butadiene rubber and silica affinity-modified solution styrene butadiene rubber may be used. . The mixing weight ratio is not particularly limited, and is not limited to the weight ratio of 1:10 in the experimental example described later. This is because it is important how many parts by weight of the carbon nanomaterial are included in the rubber composition according to the present invention. If less than 1 part by weight of carbon nanomaterials is included, the effect of improving wear resistance cannot be obtained substantially, and if more than 8 parts by weight of carbon nanomaterials are included, uniform dispersion of carbon nanomaterials is not achieved, resulting in poor wear resistance. Rather, it may deteriorate.

The carbon nanotube is at least one type of carbon nanotube selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, and multi-walled carbon nanotubes, with a purity of 90% or more, a length of 20 to 70 μm, and , the diameter is preferably 10 to 20 nm.

Graphene preferably has a purity of 95% or more, a thickness of 10 nm or less in a direction perpendicular to the carbon atomic layer, and a specific surface area (BET) of 150 to 2600 m ² /g.

4. Natural rubber

The rubber composition for a shoe outsole according to the present invention may further include natural rubber, if necessary. Natural rubber can be used to improve processability, cost, and general mechanical properties of rubber. However, it is preferable to use natural rubber within a range that does not greatly impair abrasion resistance and slip resistance. Natural rubber can be used in the range of 30 parts by weight or less (exceeding 0 parts by weight) by partially replacing the above-mentioned butadiene rubber and/or styrene butadiene rubber, if necessary.

5. Fillers

It is preferable to use 40 to 70 parts by weight of the filler. Among the fillers, silica may be used for the purpose of improving slip resistance of rubber for shoe outsoles and improving physical properties such as tensile strength, tear strength and hardness of rubber. It is preferable to use silica having a specific surface area of 120 to 220 m ² /g for BET and 100 to 250 m ² /g for CTAB. As the filler, only silica can be used, but it can also be used in combination with carbon black if necessary. It is preferable to use a silica content of 80% by weight or more and a carbon black content of 20% by weight or less in the total filler. When using more than 20% by weight of carbon black, slip resistance on wet or icy road surfaces may deteriorate. When the content of natural rubber is very small or not used, and when the content of silica-compatible rubber is high, it is preferable to lower the amount of carbon black as much as possible.

6. Preparation of rubber specimens for shoe outsoles

Rubber specimens for shoe outsoles of Examples 1 to 3 and Comparative Examples 1 to 5 were prepared in the contents shown in [Table 1]. In [Table 1], the units of each numerical value are parts by weight. More specifically, after kneading the rubber compositions for shoe outsoles of Examples 1 to 3 and Comparative Examples 1 to 5 using a Banbari mixer, a vulcanizing agent and a vulcanization accelerator were added in an open roll mill and uniformly A sheet was prepared by dispersing, and a rubber specimen for shoe outsole was prepared by press molding for an optimal vulcanization time (t90) measured by a vulcanization time meter under conditions of 160° C. and 150 kg/cm ² .

The shoe outsole rubber compositions of Examples 1 to 3 and Comparative Examples 1 to 5 commonly include 45 parts by weight of silica, 4.5 parts by weight of a silane coupling agent, 10 parts by weight of an organic material such as an anti-aging agent, and 4 parts by weight of a vulcanizing agent and a vulcanization accelerator. do. The nanocomposite material mentioned in [Table 1] means a carbon nanotube wet master batch, and the types and characteristics of each rubber and carbon nanotubes mentioned in [Table 1] are [Table 2] to [Table 4]. Same as

division comparative example
One Comparative Example 2 Comparative Example 3 Example
One Example
2 Example
3 comparative example
4 comparative example
5 Denatured BR - 80 75 70 30 - - - Normal BR 70 - - - - - - - Modified SBR - 20 20 20 20 20 15 10 Normal SBR 20 - - - - - - - nanocomposite material 11 - 5.5 11 55 88 93.5 99

division catalyst silica affinity
functional group cis content
(weight%) weight average
molecular weight distribution Denatured BR neodymium polyorganosiloxane group 98 2.1 to 3.1 Normal BR nickel X 96 5.0 to 6.0

division type silica affinity
functional group Styrene
content
(weight%) vinyl
content
(weight%) Tg
(℃) weight average
Molecular Weight
distribution Modified SBR SSBR hydroxyl group 15 30 -60 or less 1.3 to 3.0 Normal SBR ESBR X 23.5 15 -50
to -40 2.7
~ 4.3

division type Diameter (nm) Length (μm) water carbon nanotube single wall 10 to 15 30 to 50 95% or more

Example 1

The rubber specimen of Example 1 includes 70 parts by weight of neodymium silica affinity modified butadiene rubber (hereinafter, modified BR) having excellent abrasion resistance, slip resistance, excellent low temperature performance, and glass transition temperature of less than -50 ° C. Silica affinity modification Solution Styrene butadiene rubber (hereafter, modified SBR) 20 parts by weight, nanocomposite material that improves mechanical strength and wear resistance, that is, carbon nanotube wet master batch 11 parts by weight (= modified BR 10 parts by weight and carbon nanotube 1 part by weight) includes

Example 2

The rubber specimen of Example 2 included 30 parts by weight of modified BR, 20 parts by weight of modified SBR, and 55 parts by weight of a nanocomposite material (= 50 parts by weight of modified BR and 5 parts by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

Example 3

The rubber specimen of Example 3 included 20 parts by weight of modified SBR and 88 parts by weight of nanocomposite material (= 80 parts by weight of modified BR and 8 parts by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

Comparative Example 1

The rubber specimen of Comparative Example 1 includes 70 parts by weight of regular BR, 20 parts by weight of regular SBR, and 11 parts by weight of a nanocomposite material (= 10 parts by weight of regular BR and 1 part by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of BR is 80 parts by weight and the total content of SBR is the same in that the total content is 20 parts by weight, but the BR and SBR of Example 1 are modified BR and modified SBR, and Comparative Example The BR and SBR of 1 are different in that they are normal BR and normal SBR.

Comparative Example 2

The rubber specimen of Comparative Example 2 includes 80 parts by weight of modified BR and 20 parts by weight of modified SBR, and does not contain a nanocomposite material. Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

Comparative Example 3

The rubber specimen of Comparative Example 3 included 75 parts by weight of modified BR, 20 parts by weight of modified SBR, and 5.5 parts by weight of a nanocomposite material (= 5 parts by weight of modified BR and 0.5 parts by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

Comparative Example 4

The rubber specimen of Comparative Example 4 included 15 parts by weight of modified SBR and 93.5 parts by weight of nanocomposite material (= 80 parts by weight of modified BR, 5 parts by weight of modified SBR, and 8.5 parts by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

Comparative Example 5

The rubber specimen of Comparative Example 5 includes 10 parts by weight of modified SBR and 99 parts by weight of nanocomposite material (= 80 parts by weight of modified BR, 10 parts by weight of modified SBR, and 9 parts by weight of carbon nanotubes). Compared to the composition of Example 1, the total content of modified BR in the specimen is 80 parts by weight and the total content of modified SBR is 20 parts by weight, which is the same.

7. Characteristic measurement and evaluation of rubber specimens for shoe outsoles

Specific gravity, hardness, tensile strength, elongation, abrasion resistance, and slip resistance (dry conditions and wet conditions) of the shoe outsole rubber specimens of Examples 1 to 3 and Comparative Examples 1 to 5 were measured. The measurement standards are as follows, and the measurement results are shown in [Table 5].

1) Specific gravity: measured according to KS M 6519.

2) Hardness: measured using a Shore A hardness tester in accordance with KS M 6518.

3) Tensile strength: After making a thickness of about 2 mm, a test piece was prepared with a KS No. 3 cutter and measured according to KS M 6518.

4) Elongation: After making it about 2 mm thick, a test piece was prepared with a KS No. 3 cutter and measured according to KS M 6518.

5) Abrasion resistance: measured according to KS M ISO 4649:2010 (A-Method).

6) Anti-slip performance: The flooring material was measured according to ASTM D 1894-11 with stainless steel.

Comparing the measurement results of Comparative Example 1 and Example 1, it can be confirmed that both abrasion resistance and slip resistance of the rubber for shoe outsoles are improved by adopting modified BR and modified SBR as rubber base materials.

Comparing the measurement results of Comparative Example 2 and Example 1, it can be confirmed that both abrasion resistance and slip resistance of the rubber for shoe outsole are improved by adding the nanocomposite material to the rubber composition.

Further comparing the measurement results of Comparative Example 1 and Comparative Example 2, the wear resistance and slip resistance measurement results of Comparative Example 1 including nanocomposite materials adopting general BR and general SBR as rubber substrates, but modified BR and general SBR as rubber substrates. It can be seen that it is relatively better than the abrasion resistance and slip resistance measurement results of Comparative Example 2, which adopts modified SBR but does not contain nanocomposite material. According to this, in order to improve wear resistance and slip resistance, it can be said that the addition of the nanocomposite material is relatively more important than the selection of the rubber base material.

Comparing the measurement results of Comparative Example 3 and Example 1, it was found that both the abrasion resistance and slip resistance of the rubber for shoe outsoles were improved by adding 10 parts by weight of modified BR and 11 parts by weight of the nanocomposite material of 1 part by weight of carbon nanotubes to the rubber composition. You can check.

Further comparing the measurement results of Comparative Example 1 and Comparative Example 3, the abrasion resistance and slip resistance measurement results of Comparative Example 1, which did not adopt modified BR and modified SBR as rubber base materials, compared to those using modified BR and modified SBR as rubber base materials. It can be seen that it is relatively better than the abrasion resistance and slip resistance measurement results of Example 3. According to this, it is important to adopt modified BR and modified SBR as rubber base materials to improve wear resistance and slip resistance, and to add nanocomposite materials in an amount capable of improving wear resistance and slip resistance even when nanocomposite materials are added. can

Further comparing the measurement results of Comparative Example 2 and Comparative Example 3, it can be confirmed that the addition of the nanocomposite material does not necessarily improve wear resistance and slip resistance. More specifically, the abrasion resistance measurement results of Comparative Example 2 and Comparative Example 3 are the same. In the case of Comparative Example 3, the slip resistance in dry conditions was slightly improved by the addition of the nanocomposite material, but the slip resistance in wet conditions was slightly lowered. According to this, as described above, even if the nanocomposite material is added, it can be said that it is important to add the nanocomposite material in an amount capable of improving wear resistance and slip resistance.

Comparing the measurement results of Comparative Examples 2 and 3 with the measurement results of Example 1, when 5.5 parts by weight of the nanocomposite material was added, the effect of improving wear resistance and slip resistance, as described above, was not substantially , It can be confirmed that by adding 11 parts by weight of the nanocomposite material, the effect of improving wear resistance and slip resistance was substantially shown.

Comparing the measurement results of Example 1 with the measurement results of Examples 2 and 3, it can be confirmed that wear resistance and slip resistance are further improved by adding 55 parts by weight and 88 parts by weight of the nanocomposite material.

Comparing the measurement results of Example 3 and Comparative Example 4, when 93.5 parts by weight of the nanocomposite material was added, it could be confirmed that both wear resistance and slip resistance were reduced.

Comparing the measurement results of Comparative Example 4 and Comparative Example 5, when 99 parts by weight of the nanocomposite material was added, abrasion resistance and slip resistance in wet conditions were improved, but slip resistance in dry conditions was slightly reduced. The abrasion resistance and slip resistance of Comparative Examples 4 and 5 can be evaluated as equivalent to those of Examples 1 and 2, but in the case of Comparative Examples 4 and 5, especially in the case of Comparative Example 5, the hardness is high and hard However, because of its low elongation and low flexibility, it is a rubber specimen that is not suitable for actual application to shoe outsoles. Hereinafter, the tensile strength and elongation measurement results will be reviewed.

Comparing the tensile strengths of Comparative Examples 2 and 3, Examples 1 to 3 and Comparative Examples 4 and 5, the tensile strength tends to increase with the addition and increase of the nanocomposite material, but 93.5 parts by weight of the nanocomposite material is added. It can be seen that the tensile strength decreased in Comparative Example 4, and the tensile strength increased in Comparative Example 5 in which 99 parts by weight of the raw material was added.

Comparing the elongation rates of Comparative Examples 2 and 3, Examples 1 to 3 and Comparative Examples 4 and 5, the elongation decreased by the addition of the nanocomposite material and increased by the increase in the amount of the nanocomposite material, then the nanocomposite material It can be seen that the elongation rate decreases again by the additional increase of .

Although the present invention has been described in detail through representative embodiments, those skilled in the art will understand that various modifications are possible to the above-described embodiments without departing from the scope of the present invention. will be. Therefore, the scope of the present invention should not be limited to the described embodiments and should not be defined, and should be defined by all changes or modifications derived from the claims and equivalent concepts as well as the claims to be described later.

Claims (7)

Based on 100 parts by weight of the entire rubber base material,
60 to 90 parts by weight of silica affinity modified butadiene rubber (BR);
10 to 40 parts by weight of silica affinity modified solution styrene butadiene rubber (S-SBR);
40 to 70 parts by weight of a silica-containing filler; and
1 to 8 parts by weight of at least one carbon nanomaterial selected from the group consisting of carbon nanotubes, graphite, and graphene;
The carbon nanomaterial is pre-mixed with the silica-affinity-modified butadiene rubber, the silica-affinity-modified solution styrene-butadiene rubber, or a mixed rubber thereof to form a wet master batch. Rubber for shoe outsoles with excellent abrasion resistance and slip resistance composition.
According to claim 1,
The silica affinity modified butadiene rubber is NDBR (Neodymium-Butadiene Rubber) having a sheath content of 95% by weight or more and a weight average molecular weight distribution (MWD) of 2.1 to 3.1,
The silica affinity modified solution styrene-butadiene rubber has a styrene unit content of 15 to 30% by weight, a vinyl unit content of 30% by weight or more, a glass transition temperature of less than -50.0 ° C, and a weight average molecular weight distribution (MWD) of 1.3 to 30% by weight. 3.0, a rubber composition for shoe outsoles with excellent abrasion resistance and slip resistance.
According to claim 2,
The silica affinity modified butadiene rubber and the silica affinity modified solution styrene butadiene rubber,
At least one selected from the group consisting of a polyorganosiloxane group, a hydroxyl group-containing polyorganosiloxane group, an alkoxysilyl group, a hydroxyl group, an aldehyde group, a carboxyl group, an amino group, an imino group, an epoxy group, an amide group, a thiol group, and an ether group. A rubber composition for a shoe outsole having excellent abrasion resistance and slip resistance, comprising a functional group of a species.
According to claim 1,
The carbon nanotubes,
At least one kind of carbon nanotube selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes,
A rubber composition for a shoe outsole having a purity of 90% or more, a length of 20 to 70 μm, and a diameter of 10 to 20 nm, excellent wear resistance and slip resistance.
According to claim 1,
The graphene is
A rubber composition for shoe outsoles with excellent abrasion resistance and slip resistance, having a purity of 95% or more, a thickness of 10 nm or less in a direction perpendicular to the carbon atomic layer, and a specific surface area (BET) of 150 to 2600 m ² /g. .
According to claim 1,
More than 0 and 30 parts by weight of 100 parts by weight of the total rubber base material include natural rubber instead of the silica affinity modified butadiene rubber, the silica affinity modified solution styrene butadiene rubber, or a mixture rubber thereof, wear resistance and slip resistance This excellent rubber composition for shoe outsoles.
According to claim 2,
The carbon nanomaterial is pre-mixed with the silica affinity-modified butadiene rubber, the silica affinity-modified solution styrene-butadiene rubber, or a mixture rubber thereof in a weight ratio of 1:10 to form a wet master batch, wear resistance and slip resistance A rubber composition for shoe outsole with excellent performance.