KR100618030B1 - Surface modification rubber solution and therefor manufacturing of shoe sole - Google Patents

Abstract

The present invention relates to a rubber solution for shoe outsole surface modification and a method for producing a shoe outsole using the same. More specifically, the present invention relates to a three-component rubber mixture in which rubber components and amounts of rubber constituting the rubber shoe sole solution are adjusted. By using an organic solvent having rubber solubility, it is possible to obtain a rubber solution in which the intermolecular friction coefficient is maximized as the rubber intermolecular spacing is expanded by dissolution or swelling of the molecules constituting the rubber component. It can be manufactured by directly injecting into rubber compound or by applying liquid form on the surface of shoe insole or in sheet form, and then vulcanizing to improve the wear out and slip resistance of shoe outsole by applying various methods. Rubber solution for surface modification of shoe outsole It relates to a method of manufacturing the outsole.

Rubber, Thinner, Abrasion Resistant, Slip Resistant

Description

Surface modification rubber solution and therefor manufacturing of shoe sole

The present invention relates to a rubber solution for shoe outsole surface modification and a shoe outsole manufacturing method using the same, and more particularly, to a three-component rubber mixture in which the rubber component and the amount of rubber constituting the rubber shoe sole solution are adjusted. By using an organic solvent having solubility, a rubber solution in which the intermolecular friction coefficient is maximized can be obtained according to the expansion of the rubber intermolecular spacing by dissolution or swelling of the molecules constituting the rubber component. Rubber solution for surface modification of shoe outsole that can improve the wear resistance and slip resistance of the shoe outsole by applying the method to manufacture the shoe outsole by applying it directly to the rubber compound or applying it to the surface and vulcanizing it. It is about a method.

In general, shoe outsoles can be roughly divided into rubber outsoles, polyurethane-based solid outsoles and foamed outsoles.

The most widely used rubber outsole includes rubber, reinforcing fillers, vulcanizing agents and vulcanization accelerators as components, compounding them using processing equipment such as kneaders, rolls, or short-barriers and then vulcanizing them using presses. do. Natural rubber (NR; natural rubber), butadiene rubber (BR; Butadiene rubber), styrene butadiene rubber (SBR: Styrene butadiene rubber), nitrile butadiene rubber (NBR; Nitrile Butadiene Rubber) and the like are most used.

The most demanded performance of these shoe outsoles is wear resistance and slip resistance. At this time, wear resistance refers to the properties of the durability of the shoes, slip resistance refers to the slipperiness and grip properties of the shoes, the wear resistance and slip resistance described above is the most important factor in the outsole of the shoes and many researches on this have.

Until now, in order to improve slip resistance of shoe outsoles, isobutyl isoprene rubber (IIR) having excellent slip resistance is used alone, or a large amount of such butyl rubber is added to the rubber composition. Is applying. In addition, in order to improve the wear resistance and mechanical strength of the shoe outsole, a method of adding a large amount of white carbon or carbon black as a reinforcing filler appropriate for the application is applied.

However, abrasion resistance and slip resistance are contrary concepts, and as wear resistance increases, slip resistance decreases, so it is always necessary to find a compromise that is suitable for shoe use. Recently, such a compromise has reached its limit.

For example, butyl rubber and other rubbers having excellent slip resistance do not have good wear resistance, and thus, when blending the above slip resistant rubbers to improve the slip resistance of the rubber outsole rubber composition, wear resistance is inevitably degraded. will be.

Therefore, according to the shoe outsole manufacturing technology up to now it is recognized that it is impossible to manufacture a shoe outsole that maximizes the wear resistance and slip resistance at the same time.

Accordingly, the inventors of the present invention have tried to develop a shoe outsole with excellent wear resistance and slip resistance at the same time, and as a result, the rubber component and butadiene rubber or modified butadiene rubber used in rubber-based shoe outsole such as natural rubber, and butyl rubber When the rubber solution containing a three-component rubber mixture, and a diluent capable of dissolving the rubber component is added or surface-coated to an existing rubber-based shoe outsole compound, the rubber surface modification effect was found to be excellent and completed the present invention. .

Accordingly, an object of the present invention is to provide a shoe outsole which is directly used in a rubber compound for shoe outsole or by applying a vulcanization process after applying it to a surface while maintaining the wear resistance of the shoe outsole while improving slip resistance.

The present invention is 10 to 50% by weight of one or two or more mixtures selected from natural rubber, isoprene rubber, styrene butadiene rubber, nitrile butadiene rubber and carboxynitrile nitrile butadiene rubber, butadiene rubber, modified butadiene rubber or mixtures thereof 20 to 60 Shoe surface modification rubber comprising a three-component rubber mixture comprising 5 wt% and 5 to 40 wt% butyl rubber, and 50 to 10000 parts by weight of a diluent and 5 to 50 parts by weight of an additive based on 100 parts by weight of the three-component rubber mixture. Characterized by a solution.

The present invention provides a rubber by dissolving or swelling molecules constituting the rubber component by using an organic solvent having rubber solubility as a diluent in a three-component rubber mixture in which the component and the amount of rubber constituting the rubber shoe sole solution are controlled. According to the expansion of the intermolecular spacing, a rubber composition with a maximized intermolecular friction coefficient can be obtained, which is directly added to a rubber compound for shoe soles already prepared, applied as a liquid to the surface, or manufactured in a sheet form and vulcanized. The present invention relates to a rubber solution for shoe surface modification for producing a shoe outsole that can improve abrasion resistance and slip resistance at the same time, and a method of manufacturing a shoe outsole using the same.

This invention will be described in detail.

The rubber solution for shoe surface modification of the present invention is characterized by using a three-component rubber mixture as a rubber component and selecting a type of diluent, so that the intermolecular distance of the rubber surface can be controlled by the configuration of the present invention. It is.

The rubber solution for shoe surface modification of the present invention is 10-50% by weight of one or two or more mixtures selected from natural rubber, isoprene rubber, styrene butadiene rubber, nitrile butadiene rubber, and carboxyl nitrile butadiene rubber with good processability and wear resistance. Three-component rubber mixtures comprising 20 to 60% by weight of good butadiene rubber, modified butadiene rubber or mixtures thereof and 5 to 40% by weight of butyl rubber having excellent slip resistance. If the amount of the butadiene rubber, the modified butadiene rubber, or a mixture thereof is less than 20% by weight, the wear resistance is lowered, and if it exceeds 60% by weight, the slip resistance is lowered. In addition, when the amount of butyl rubber used is less than 5% by weight, it is not excellent in slip resistance, and when it exceeds 40% by weight, wear resistance is remarkably decreased.

The diluent used to dissolve the above-mentioned three-component rubber mixture is a solvent having rubber solubility, a high solubility solvent selected from toluene, xylene, methyl isobutyl ketone, hexane and acetone, an acetate solvent such as methyl acetate, ethyl acetate, Alcohol solvents, such as ethanol and butanol, can be selected and used.

The amount of such a diluent is 50 to 10000 parts by weight based on 100 parts by weight of the three-component rubber mixture. When the amount is less than 50 parts by weight, workability is lowered, and when it is more than 10000 parts by weight, slip resistance is reduced. When kneading by adding a diluent to the three-component rubber mixture, rubber molecules swell or dissolve to widen the space between molecules, thereby maximizing the inter-molecular friction coefficient, thereby imparting the desired physical properties in the present invention. .

The rubber solution for shoe surface modification of the present invention may include additives conventionally used in the art in addition to the rubber component and the diluent described above.

Although it does not limit as such an additive, Specifically, for example, 5-20 weight part of reinforcement materials, 1-10 weight part of plasticizers, 0.1-5 weight part of silane coupling agents, 0.5-5 weight part of vulcanizing agents, 0.5-5 vulcanization accelerators It is preferable to use one selected from parts by weight, 0.1 to 4 parts by weight of antioxidant, and the total amount of additive to be used by 5 to 50 parts by weight.

In particular, the diluent and the plasticizer as a component having the property of swelling or dissolving the rubber component, it is preferable to use a material that can be volatilized at 80 ℃ or less.

When the rubber composition for shoe surface modification of the present invention having the above components and contents is applied (coated) to a conventional outsole rubber compound, the surface of the outsole is vulcanized, thereby reducing slip resistance without reducing the wear resistance of the rubber compound. It can be maximized, and a method of directly vulcanizing the diluent to the rubber compound is also applicable.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the following Examples.

Comparative Examples 1-3: Production of Existing Shoe Soles

Next, a rubber composition comprising the components and contents as shown in Table 1 was kneaded at room temperature using a kneader, and then manufactured into a sheet of 3 to 5 mm, which was press-molded at 155 ° C. for 8 minutes to provide slip resistant shoe outsole. Was prepared.

division Comparative Example 1 Comparative Example 2 Comparative Example 3 weight% NR 30 20 - BR 50 70 - NBR - 10 - IIR 20 - 100 Parts by weight ZnO 4 5 4 Stearic acid One One One PEG - 3 - Silica - 35 - Carbon black 50 - 50 Si-69 - 0.5 - W1500 8 5 8 BHT One One One DM 1.5 1.5 - M 0.5 0.5 0.5 TT One 0.5 One sulfur 2.6 2.5 2.5 NR: Natural Ruber, BR: Butadiene Rubber, NBR: Nitrile Butadiene Rubber, IIR: Isobutyl Isoprene Rubber, PEG: Poly Ethylene Glycol, Silica: Zeosil 155 [Rhodia], Carbon Black: ISAF [KCB] Si-69 [Degussa], W1500 [Unchanged petroleum], BHT: Butylated hydroxy toluene, DM: Dibenzothiazyl disulfide, M: Mercaptobenzothiazole, TT: Tetramethyl thiuram disulfide The above parts by weight represent the relative usage of the rubber composition relative to 100 parts by weight.

Examples 1-2: Preparation of rubber solution for surface modification and shoe outsole applying the same

3,500 parts by weight of hexane (n-hexane), 1,500 parts by weight of toluene as a diluent, based on 100 parts by weight of a three-component rubber mixture consisting of 20% by weight of natural rubber, 40% by weight of butadiene rubber and 40% by weight of butyl rubber 5 parts by weight of Aerosil 200 (degussa), 5 parts by weight of conventional vulcanization and vulcanization accelerator and 7 parts by weight of conventional additives (4 parts by weight of zinc oxide, 1 part by weight of stearic acid, 2 parts by weight of polyethylene glycol 4000) By stirring at high speed for 1 hour at a speed of 3000 RPM at room temperature to prepare a rubber solution for surface modification of the present invention.

The prepared surface modification rubber solution was applied to the compound sheets (3 to 5 mm) of Comparative Examples 1 and 2 at 0.1 to 0.5 mm (dry thickness), dried at room temperature for 4 hours, and then pressed at 155 ° C. for 8 minutes. Molding to prepare Examples 1 and 2, respectively.

Experimental Example: Measurement of Physical Properties

The physical properties of the shoe outsole manufactured by Examples 1 to 2 and Comparative Examples 1 to 3 were measured and shown in the following Table 2.

Hardness was tested according to KSM3043, tensile strength, elongation rate and tear strength were tested according to ASTM D412, and wear was measured using an NBS wear tester. Slip resistance was measured in both dry and wet conditions by static slip tester (SLH type slip tester) and dynamic slip tester (Dynamic friction tester, Davenport), respectively.

 Properties unit Comparative Example 1 Comparative Example 2 Comparative Example 3 Example 1 Example 2 Hardness Shore a 67 67 66 67 67  Sp. Gr. - 1.10 1.16 1.17 1.10 1.16 The tensile strength kgf / ㎠ 110 160 89 110 160 Elongation % 300 450 620 300 460 Tear strength kgf / cm 45 55 31 45 53 Abrasion Degree (NBS) % 350 750 60 350 710 Slip resistance silence dry ° 62 62 64 68 64 Wetting ° 44 34 56 51 51 dynamic dry kgf / ㎠ 32 35 45 42 38 Wetting kgf / ㎠ 18 16 21 26 24

As shown in Table 2, Examples 1 to 2 to which the rubber solution for surface modification of the present invention is applied can be seen that both static and dynamic slip resistance are improved while maintaining excellent wear resistance.

In particular, it exhibits slip resistance similar to that of Comparative Example 3 in which butyl rubber alone has the best slip resistance and has excellent wear resistance.

As described above, the rubber solution for surface modification of the present invention has the effect of maximizing the coefficient of intermolecular friction by adjusting the interval of the rubber molecular chain, thereby controlling the slip resistance of the outsole to which it is applied.

Therefore, the shoe outsole using the conventional compounding technology has the advantage of manufacturing a shoe outsole excellent in both wear resistance and slip resistance that can not be realized.

In addition, no special processing equipment is required, and a simple method of coating a surface of a conventional rubber compound without significantly modifying the existing manufacturing method of the shoe outsole can maximize the slip resistance of the shoe outsole.

Claims (4)

Natural rubber, isoprene rubber, styrene butadiene rubber, nitrile butadiene rubber, and carboxyl nitrile butadiene rubber, 10 to 50% by weight of one or two or more mixtures selected from the group consisting of butadiene rubber, modified butadiene rubber, or a mixture thereof 20 to 60% by weight; and A three-component rubber mixture containing 5 to 40% by weight of butyl rubber, A rubber solution for shoe surface modification comprising 5 to 10000 parts by weight of a diluent and 5 to 50 parts by weight of an additive based on 100 parts by weight of the three-component rubber mixture. The shoe surface according to claim 1, wherein the diluent is one or a mixture of two or more selected from a high-solubility solvent, an acetate solvent, and an alcohol solvent selected from toluene, xylene, methyl isobutyl ketone, hexane, and acetone. Rubber solution for reforming. The method of claim 1, wherein the additive is contained in 5 to 20 parts by weight of the reinforcing material, 0.01 to 5 parts by weight of the silane coupling agent, 0.5 to 5 parts by weight of the vulcanizing agent, 0.5 to 5 parts by weight of the vulcanization accelerator, and 0.1 to 5 parts by weight of the antioxidant. Rubber solution for the surface modification of the shoe, characterized in that selected. The method of manufacturing a shoe outsole, characterized in that the rubber solution of any one of claims 1 to 3 directly added to the existing unvulcanized rubber compound or applied to the surface and then vulcanized.