KR101156575B1 - Composition for outsole and outsole manufactured by using the same - Google Patents

Abstract

PURPOSE: An anti-slip outsole composition and an outsole which is manufactured by using thereof are provided to maximize hysteresis friction force, thereby improving anti-slip property, durability, and abrasion resistance. CONSTITUTION: An anti-slip outsole composition comprises 100.0 parts by weight of polymeric material, 0.1-20 parts by weight of clay mineral, 0.5-10 parts by weight of anion-based surface modification agent, and 0.05-60 parts by weight of cross-linking agent. The anion-based surface modification agent is one selected from polyoxyethylene nonylphenyl ether, lauryl POE(3) phosphoric acid, sodium dioctyl sulfosuccinate, sodium dialkyl sulfosuccinate, and a combinations thereof. The clay mineral is one selected from kaolinite, dicanite, halloysite, montmorillonite, bentonite, acid clay, illite, glauconite, and a combination thereof.

Description

Composition for shoe outsole and shoe outsole manufactured using the same TECHNICAL FIELD

The present invention relates to a shoe outsole composition and a shoe outsole manufactured using the same. More specifically, the hysteresis friction is maximized to provide an excellent anti-slip effect, while the weight is reduced, the durability and wear resistance are greatly improved, and the weight is reduced. In accordance with the present invention relates to a slip resistant shoe outsole composition and a shoe outsole manufactured using the same.

Outsole is the part that is most sensitive to the external conditions such as the condition and characteristics of the ground by direct contact with the ground and its effect is primarily transmitted. These outsoles should be able to improve the driving efficiency and prevent physical injuries by appropriately responding to the ground conditions when walking or running, especially when the road surface is wet by snow or rain due to climate change. Function is even more important.

However, existing shoe outsoles do not have adaptability to these various external environments and only depend on mechanical properties such as tensile, tear strength and wear resistance. In addition, by seeking a non-slip function only by the pattern design of the outsole, there is a disadvantage that the slip prevention function is not maximized when exposed to a special external environment, such as when climbing or working in a special workplace. In addition, when the tackifier is applied to give the surface of the outsole, the effect may be exerted when used indoors. However, when moisture is present on the bottom surface such as when climbing, the effect is not exerted. Over time, the stickiness may disappear.

In order to solve the above problem, the inventors of the Korean Patent Registration No. 10-0614887 “Low-weight Slip-resistant Shoe Sole Composition Using Slow Recovery Characteristics of Polymers”, greatly improving hysteresis friction between the ground and the outsole in a dry state. In addition to the anti-slip effect, in particular, a shoe outsole composition expressing the anti-slip effect in the wet state has been provided.

On the other hand, butyl rubber (IIR: Isobutyl isoprene Rubber) used as a rubber material exhibiting slow recovery characteristics has an isobutyl structure as a main chain, and commercially available butyl rubber has a low isoprene content of about 2.5% or less. Accordingly, due to the high internal friction characteristics and low crosslinking degrees, recovery from deformation is slow. Therefore, when the butyl rubber is used as a shoe outsole and grounded with irregular ground, a certain level of deformation occurs on the surface of the outsole due to the load of the human body, and the contact between the ground and the outsole due to a relatively slow recovery speed after general deformation occurs. The area can be secured easily, leading to an improvement in frictional force due to adhesion associated with the contact area.

However, butyl rubber has low wear performance due to heat accumulation due to deformation and recovery due to high internal friction, low crosslinking degree, and high friction coefficient which is directly related to wear. In the case of outsole, it is often economical to have a grate depending on the frequency of use, and it has a risk of injury because it does not express anti-slip performance due to outsole wear during hiking.

In addition, when styrene-based block copolymers and solution-polymerized styrene / butadiene rubbers used as rubber materials exhibiting slow recovery characteristics are used as base materials, they have higher abrasion resistance than butyl rubber alone, but have a lower crosslinking degree for expression of slow recovery characteristics. It should be kept at a level and thus has a low wear resistance compared to a rubber composition for shoe outsoles.

Thus, in order to improve the low wear resistance of rubber compositions exhibiting slow recovery properties, natural rubbers or synthetic rubbers having a high degree of unsaturation are generally combined with butyl rubber to provide a mixture. However, when mixed with rubber having a high degree of unsaturation, there is a problem that the crosslinking balance is broken, tensile strength and tearing strength are lowered, rubber elasticity is high, deformation recovery is faster, and the anti-slip performance is lowered.

Or, there is a method of improving the wear resistance by applying a glass fiber to produce a composite material composition. Through this method, the wear resistance of the rubber composition expressing the slow recovery characteristics can be improved, but when the glass fiber is added at the time of blending, scratches are generated on the surface of the processing equipment, thereby shortening the life of the processing equipment.

Republic of Korea Patent No. 10-0614887 (Registration Date: August 16, 2006) Republic of Korea Patent No. 10-0693451 (Registration Date: January 8, 2007)

An object of the present invention is to provide a shoe sole composition that can maximize the hysteresis friction is excellent anti-slip effect, greatly reduced durability and wear resistance while reducing weight, and can reduce the wearer's fatigue as the weight is reduced will be.

Another object of the present invention is to provide a shoe outsole made of the composition for the outsole.

In order to achieve the above object, according to an embodiment of the present invention, 100 parts by weight of polymer material, 0.1 to 20 parts by weight of clay mineral, 0.5 to 10 parts by weight of anionic surface modifier, and 0.05 to 60 parts by weight of crosslinking agent Provided is a shoe sole composition.

The clay mineral may be any one selected from the group consisting of kaolinite, decite, halloysite, montmorillonite, bentonite, acidic clay, illite, haeolite and combinations thereof.

The clay mineral may have an average particle diameter of 0.1 to 10um.

The clay mineral is dimethyl dihydrogenated tallow quaternary ammonium (dimethyl, dihydrogenated tallow, quaternary ammonium, 2M2HT), methyl dihydrogenated tallow ammonium (methyl, dihydrogenated tallow ammonium, M2HT) 2-ethylhexyl quaternary ammonium (dimethyl, hydrogenated tallow, 2-ethylhexyl quaternary ammonium, 2MHTL8) and may be surface treated with any one selected from the group consisting of a combination thereof.

The clay mineral may be surface treated with 50 to 150 mEq / 100 g (clay).

The anionic surface modifying agent is polyoxyethylene nonylphenyl ether, lauryl sampioic phosphoric acid (lauric POE (3) Phosphoric acid; POE: polyoxyethylene), sodium dioctyl sulfosuccinate ), Sodium dialkyl sulfosuccinate, and combinations thereof.

The polymer material may include any one selected from the group consisting of styrene block copolymers, solution-polymerized styrene / butadiene rubbers, butyl rubbers, natural rubbers, and combinations thereof.

The polymer material may include 20 to 40 parts by weight of a styrenic block copolymer, 10 to 30 parts by weight of solution-polymerized styrene / butadiene rubber, 30 to 50 parts by weight of halogenated butyl rubber, and 0 to 20 parts by weight of natural rubber.

The styrenic block copolymer may be a double or triple block copolymer consisting of a hard block and a soft block.

The hard block is polystyrene, and the soft block is composed of 3,4-polyisoprene, polybutadiene, hydrogenated 3,4-polyisoprene, hydrogenated polybutadiene and combinations thereof having a glass transition temperature of -20 to 30 ° C. It may be any one selected from the group.

The solution-polymerized styrene / butadiene rubber may have a glass transition temperature of -40 to 20 ° C.

The butyl rubber is a copolymer of isobutylene and isoprene, and may have an unsaturation of 0.6 to 2.5 mol%.

The butyl rubber is any one selected from the group consisting of chlorinated-isobutylene isoprene rubber (CIIR), brominated isobutylene-isoprene rubber (BIIR), and combinations thereof. It may be one halogenated butyl rubber.

The crosslinking agent may be any one selected from the group consisting of a sulfur crosslinking agent, an organic peroxide crosslinking agent, a resin crosslinking agent, and a combination thereof.

The shoe sole composition may further include any one of 3 to 100 parts by weight of a filler selected from the group consisting of silica, carbon black, calcium carbonate, talc and combinations thereof.

The shoe sole composition may be any one of rubber additives selected from the group consisting of a tackifier, an extended oil, an antioxidant, an ozonation inhibitor, a pigment, a silane coupling agent, a homogeneous compound, and a combination thereof. It may further comprise by weight.

According to another embodiment of the present invention, a shoe sole manufactured by compression molding the composition for shoe outsole for 3 to 30 minutes at a molding temperature of 100 to 200 ℃, a molding pressure of 100 to 300 kg / ㎠.

The shoe outsole made of the composition for shoe outsole of the present invention is maximized hysteresis friction to excellent anti-slip effect, greatly reduced durability and wear resistance while reducing weight, can reduce the wearer's fatigue as the weight is reduced .

Hereinafter, the present invention will be described in detail.

I. Outsole Composition

A shoe sole composition according to an embodiment of the present invention includes 100 parts by weight of a polymer material, 0.1 to 20 parts by weight of clay mineral, 0.5 to 10 parts by weight of anionic surface modifier, and 0.05 to 60 parts by weight of crosslinking agent.

The polymer material can be preferably used as long as it can express slow recovery characteristics. The polymer material capable of expressing the slow recovery characteristics may be any one selected from the group consisting of styrene-based block copolymers, solution-polymerized styrene / butadiene rubbers, butyl rubbers, natural rubbers, and combinations thereof. It is not limited to this.

In addition, the polymer material may include 20 to 40 parts by weight of styrene-based block copolymer, 10 to 30 parts by weight of solution-polymerized styrene / butadiene rubber, 30 to 50 parts by weight of halogenated butyl rubber, and 0 to 20 parts by weight of natural rubber. Preferably, it may include 25 to 35 parts by weight of the styrenic block copolymer, 15 to 25 parts by weight of solution-polymerized styrene / butadiene rubber, 35 to 45 parts by weight of halogenated butyl rubber and 5 to 15 parts by weight of natural rubber. When the polymer material includes the styrenic block copolymer, the solution-polymerized styrene / butadiene rubber, the halogenated butyl rubber and natural rubber in the content range, it may have excellent slow recovery characteristics.

The styrenic block copolymer may be a block copolymer consisting of a hard block and a soft block, and may be a double block copolymer having a hard-soft (AB type) structure or a triple block copolymer having a hard-soft-hard (ABA type) structure. Can be.

The hard block is polystyrene, and the soft block is not particularly limited as long as the glass transition temperature (Tg) is -20 to 30 ° C., 3,4-polyisoprene, polybutadiene, hydrogenated 3,4-polyisoprene, hydrogenated It may be any one selected from the group consisting of polybutadiene and combinations thereof. In addition, the polyisoprene, polybutadiene, hydrogenated 3,4-polyisoprene or hydrogenated polybutadiene may have a saturated or unsaturated structure.

The solution-polymerized styrene / butadiene rubber is not particularly limited as long as the glass transition temperature is -40 to 20 ° C, and butadiene is hydrogenated.

The butyl rubber may be butyl rubber or halogenated butyl rubber. The butyl rubber preferably has an unsaturation of 0.6 to 2.5 mol% in terms of slow recovery properties. In this case, the mole% represents the number of moles of isoprene per 100 moles of isobutylene after copolymerization.

The butyl rubber may be a copolymer of isobutylene and isoprene, and the halogenated butyl rubber may be chlorinated isobutylene isoprene rubber (CIIR), brominated isobutylene-isoprene It may be any one selected from the group consisting of rubber (Brominated Isobutylene-Isoprene Rubber (BIIR)) and combinations thereof. The chlorinated-isobutylene-isoprene rubber or the brominated-isobutylene-isoprene rubber has a hydrogen atom bonded to a carbon atom constituting a double bond of isoprene, a monomer of a copolymer of isobutylene and isoprene, or chlorine (Cl) or It is substituted with a bromine (Br) atom.

The polymer material may further include any one selected from the group consisting of natural rubber, butadiene rubber, emulsion polymerized styrene / butadiene rubber, nitrile rubber, and combinations thereof as rubbers or elastomers as polymer material aids. The polymeric material aid may be included in an amount of 0.1 to 30% by weight based on the total weight of the polymeric material.

The clay minerals include kaolin-based minerals such as kaolinite, decite, and halosite, montmorillonite-based minerals such as montmorillonite, bentonite, and acidic clay, mica such as illite, haeolite, and chlorite Or allophan and the like, and any one selected from the group consisting of kaolinite, decite, halloysite, montmorillonite, bentonite, acidic clay, illite, haeolite and combinations thereof may be preferably used. Any one selected from the group consisting of kaolinite, montmorillonite, bentonite, illite and combinations thereof can be preferably used.

The clay mineral may be included in an amount of 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, and more preferably 5 to 10 parts by weight, based on 100 parts by weight of the polymer material. When the content of the clay mineral is less than 0.1 parts by weight, the enhancement of the reinforcing effect due to the addition of the clay mineral is insignificant, and when it exceeds 20 parts by weight, difficulty in dispersion may follow.

The clay mineral may have an average particle diameter of 0.1 to 10um, preferably 1 to 6um. When the average particle diameter of the clay mineral is less than 0.1um, the scattering is severe, workability is low, it may be difficult to disperse, if it exceeds 10um may not exhibit a reinforcing effect.

The clay mineral is dimethyl dihydrogenated tallow quaternary ammonium (dimethyl, dihydrogenated tallow, quaternary ammonium, 2M2HT), methyl dihydrogenated tallow ammonium (methyl, dihydrogenated tallow ammonium, M2HT) It can be surface treated with any one selected from the group consisting of 2-ethylhexyl quaternary ammonium (dimethyl, hydrogenated tallow, 2-ethylhexyl quaternary ammonium, 2MHTL8) and combinations thereof.

The clay mineral may be surface treated with 50 to 150 mEq / 100 g (clay), preferably surface treated with 90 to 100 mEq / 100 g (clay). When the surface treatment content is less than 50mEq / 100g (clay) may be low reinforcing effect by clay minerals, low surface treatment effect, when the surface treatment content exceeds 150mEq / 100g (clay) may be a large plasticization effect.

The shoe sole composition can significantly improve durability and wear resistance as the clay mineral is included, and the clay mineral can obtain a sufficient reinforcing effect even when a small amount is used, so that the wearer wears as the weight of the shoe sole is reduced. Can reduce fatigue.

The clay mineral, in particular the montmorillonite-based clay mineral, is a silicate material having a SiO ₄ basic structure, and has a plate shape of several nm in thickness and several tens of nm in length. The clay mineral has an ion exchange capacity between the plate-like structures, and due to its hydrophilic property, is difficult to disperse in a hydrophobic polymer material, which makes it difficult to disperse when used as a reinforcing filler.

Thus, the composition for the shoe sole is the clay containing the anionic surface modifier 0.5 to 10 parts by weight, preferably 2 to 7 parts by weight, more preferably 3 to 5 parts by weight based on 100 parts by weight of the polymer material Increase the affinity between minerals and polymer materials.

The anionic surface modifier is a phosphate compound such as polyoxyethylene nonylphenyl ether, lauryl sampioic phosphoric acid (Lauryl POE (3) Phosphoric acid; POE: polyoxyethylene), sodium dioctyl sulfosuccinate It may be any one selected from the group consisting of sulfosuccinate compounds such as sodium dioctyl sulfosuccinate or sodium dialkyl sulfosuccinate, and combinations thereof.

The crosslinking agent is included in an amount of 0.05 to 60 parts by weight based on 100 parts by weight of the polymer material. When the content of the crosslinking agent is within the above range, it is possible to maximize the effect of the crosslinking agent without a significant cost increase. The crosslinking agent may be any one selected from the group consisting of a sulfur crosslinking agent, an organic peroxide crosslinking agent, a resin crosslinking agent, and a combination thereof.

Sulfur or insoluble sulfur may be used as the sulfur crosslinking agent.

In addition, when the sulfur sole composition is used as the crosslinking agent, the shoe sole composition may include 0.1 to 10 parts by weight of sulfur crosslinking agent and 0.01 to 8 parts by weight of vulcanization accelerator based on 100 parts by weight of the polymer material. The vulcanization accelerator may be any one selected from the group consisting of aldehydes, ammonia, aldehydes, amines, guanidines, thioureas, thiazoles, sulfenamides, thiurams, dithiocarbamates, and combinations thereof. Can be.

When the shoe sole composition includes an organic peroxide crosslinking agent as the crosslinking agent, the organic peroxide crosslinking agent may be included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polymer material.

The organic peroxide crosslinking agent is cyclohexanone peroxide, t-butylperoxyisopropyl carbonate, t-butylperoxylaurylate, t-butylperoxyacetate, di-t-butyldiperoxyphthalate, t-dibutylperfer Oxymaleic acid, t-butyl cumyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, dibenzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, Methyl ethyl ketone peroxide, di- (2,4-dichlorobenzoyl) peroxide, 1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2, 5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxide, 2,5-dimethyl-2,5- (t -Butylperoxy) -3-hexyne, n-butyl-4,4-bis (t-butylperoxy) valerate, α, α'-bis (t-butylperoxy) diisopropylbenzene, and their Any one selected from the group consisting of a combination There.

When the shoe sole composition includes a resin crosslinking agent as the crosslinking agent, the resin crosslinking agent may be included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polymer material. The resin crosslinking agent may be a modified phenol resin including 5 to 20 wt% of methylol groups.

The shoe sole composition may further include a general filler in addition to the clay mineral. The filler may be any one selected from the group consisting of carbon black, silica, calcium carbonate, talc and combinations thereof.

The filler may be included in 3 to 100 parts by weight based on 100 parts by weight of the polymer material. When the content of the filler is less than 3 parts by weight, the enhancement of the reinforcing effect due to the addition of the filler is insignificant, and when it exceeds 100 parts by weight, difficulty in dispersion may be followed.

The shoe sole composition may be any one of rubber additives selected from the group consisting of a tackifier, an extended oil, an antioxidant, an ozonation inhibitor, a pigment, a silane coupling agent, a homogeneous compound, and a combination thereof. It may further comprise by weight. When the content of the rubber additive is within the above range, it is possible to enhance physical properties of the shoe sole composition without significant cost increase.

The tackifier may be used to reduce the change in hardness with temperature change. The tackifier may be any one selected from the group consisting of rosin derivatives, terpene resins, petroleum resins, coumarone resins, styrene resins, phenol resins, and combinations thereof. The tackifier may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polymer material.

The extension oil may be any one selected from the group consisting of naphthenic, aromatic, or hydrocarbon-based processing oils such as paraffins, rapeseed oils, or natural oils such as castor oil, and combinations thereof. The extension oil may be included in an amount of 1 to 50 parts by weight based on 100 parts by weight of the polymer material.

Any of the antioxidants and ozonation agents can be used as long as they are used in the technical field to which the present invention belongs. In addition, the antioxidant and ozone inhibitor may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the polymer material, respectively.

The pigment is for imparting various colors to the composition for shoe soles, and any pigment can be used as long as it is used in the technical field to which the present invention belongs. In addition, the pigment may be included in 1 to 60 parts by weight based on 100 parts by weight of the polymer material.

Ⅱ. Outsole

A shoe outsole according to another embodiment of the present invention is manufactured using the shoe sole composition.

First, a polymer material, a clay mineral, an anionic surface modifier and optionally a filler and a rubber additive are mixed, and then a crosslinking agent is added to prepare a shoe sole composition. The shoe sole composition is prepared in the form of a sheet and placed in a closed mold. Thereafter, the composition for shoe soles in the form of a sheet may be compression molded for 3 to 30 minutes under a high temperature and high pressure of 100 to 200 ° C. and 100 to 300 kg / cm ² using a compression molding machine to prepare a shoe sole.

The shoe outsole can be applied not only to general shoes, but also to special shoes such as hiking boots, marine work shoes, boat shoes, and the like.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Preparation Example: Preparation of Shoe Sole Specimen Using Shoe Sole Composition

(Examples 1 to 4)

To the content shown in Table 1, the polymer material, filler, clay minerals, rubber additives and anionic surface modifiers were kneaded for 15 minutes in a sealed mixer at 110 ℃. Thereafter, the crosslinking agents were added and kneaded sufficiently in a roll mill having a surface temperature of 75 ° C. Thereafter, a 4 mm kneaded sheet was prepared and aged at room temperature (23 ° C.) for at least 24 hours. The kneaded sheet thus prepared is cut into a cavity of a mold, and then put into a mold, and then compression molded for an optimal vulcanization time (t90) measured by a vulcanization time measuring instrument under conditions of 155 ° C. and 150 kg / cm 2. A test specimen was prepared.

(Comparative Examples 1 and 2)

As shown in Table 1, except for not adding a clay mineral and an anionic surface modifier was carried out in the same manner as in Examples 1 to 4 to prepare a shoe insole.

(Examples 5 to 8)

Except for using the kaolinite in place of montmorillonite as a clay mineral in Examples 1 to 4 was carried out in the same manner as in Examples 1 to 4 to prepare a shoe insole.

(Examples 9 to 12)

Except for using the illite instead of montmorillonite as a clay mineral in Examples 1 to 4 was carried out in the same manner as in Examples 1 to 4 to prepare a shoe insole.

division Example Comparative example One 2 3 4 One 2 Polymer
Material Solution Polymerized Styrene / Butadiene Rubber ¹⁾ - - 20 20 - 20 Styrenic block copolymer ²⁾ - - 30 30 - 30 Butyl rubber ³⁾ 100 100 - - 100 - Halogenated Butyl Rubber ⁴⁾ - - 40 40 - 40 Natural rubber ⁵⁾ - - 10 10 - 10 MMT 1st MMT ⁶⁾ 5 - 10 - - - 2nd MMT ⁷⁾ - 10 - 5 - - Filler Silica ⁸⁾ - - 22 32 - 42 Carbon black ⁹⁾ 40 30 - - 50 - Anionic Surface Modifiers ¹⁰⁾ 3 5 5 3 - - Rubber
additive Tackifier ¹¹⁾ 5.0 5.0 5.0 5.0 5.0 5.0 Antioxidant ¹²⁾ 2.0 2.0 2.0 2.0 2.0 2.0 Extension oil ¹³⁾ 5.0 5.0 5.0 5.0 5.0 5.0 Silane coupling agent ¹⁴⁾ 3.0 3.0 3.0 3.0 3.0 3.0 Homogenizer ¹⁵⁾ 2.0 2.0 2.0 2.0 2.0 2.0 Activator ¹⁶⁾ 3.0 3.0 3.0 3.0 3.0 3.0 Stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 zinc oxide 5.0 5.0 5.0 5.0 5.0 5.0 Cross-linking agent sulfur 1.0 1.0 - - - 1.0 Promoter 1 ¹⁷⁾ 1.5 1.5 - - - 1.5 Accelerator2 ¹⁸⁾ 1.0 1.0 - - - 1.0 Accelerator 3 ¹⁹⁾ 1.5 1.5 - - - 1.5 Organic Peroxide Crosslinker ²⁰⁾ - - 0.5 0.5 0.5 - Crosslinking Aids ²¹⁾ - - 0.5 0.5 0.5 - Phenolic Resin Crosslinker ²²⁾ - - 2.0 2.0 2.0 - [Unit: parts by weight]
week)
1) Asahi Kasei, Asaprene
2) Kuraray, Hybrar
3) EXXON, IIR
4) EXXON, BIIR
5) SMR 3L
6) Montmorillonite with an average particle diameter of 6um and 125mEq / 100g (clay) surface treatment with 2M2HT
7) Montmorillonite with an average particle diameter of 6 μm and 95 mEq / 100 g (clay) surface treatment with 2MHTL8
8) Rhodia, Zeosil155
9) KCB, HAF (N330)
10) Sodium Dioctyl Sulfosuccinate (manufactured by Dongnam Synthetics, D0113L)
11) Cologne oil painting, Hi-korez
12) Uni Royal Chemicals, BHT
13) Michang Petrochemical, Paraffin Oil
14) Degussa, Si-69
15) Struktol, WB-215
16) Southeast Synthesis, PEG4000
17) Dongyang Steel Chemical, Oricel-M
18) Dongyang Steel Chemical, Oricel-DM
19) Dongyang Steel Chemical, Oricel-TT
20) NOF Co., DCP
21) Degussa, TAC50
22) Sovereign Chemical Co. R7510

[Test Example: Evaluation of the characteristics of the manufactured shoe outsole]

The properties of the shoe insoles prepared in Examples 1 to 12 and Comparative Examples 1 and 2 were tested in the following manner, and the results for Examples 1 to 4 and 1 and 2 in Table 2 are shown in Table 2 below. Indicated.

1) Specific gravity: In accordance with KS M6519, the measurement was performed 5 times using a model DMA-3, an automatic specific gravity measurement device of Ueshima Corporation, and the average value was taken.

2) Hardness: It was measured using an Asker A hardness tester according to KS M6518.

3) Tensile strength and elongation rate were measured using an universal testing machine of Instron according to KS M6518.

4) Tear strength: measured using a Zwick universal testing machine according to KS M6518.

5) NBS wear resistance: Using the NBS wear tester (ASTM 1630) to calculate the wear resistance as shown in Equation 1 below.

[Equation 1]

6) Rebound elasticity: Rebound elasticity was measured using the vertical rebound resilience tester of Daesung Science in accordance with ASTM D2632-96.

7) Copper Slip (Drying): The slip property in the dynamic state was measured by using the Lloyd's copper friction tester in accordance with ASTM D1897-78.

Physical Characteristics unit Example Comparative example One 2 3 4 One 2 importance - 1.14 1.12 1.13 1.15 1.16 1.18 Hardness A type 62 63 64 63 63 62 The tensile strength kg _f / cm ² 160 150 150 155 170 160 Elongation % 520 450 420 500 720 590 Phosphorus strength kg _f / cm 68 72 70 62 62 52 NBS wear resistance % 100 150 300 250 50 150 Resilience % 11 12 13 12 10 12 East Sleep μ 2.24 2.24 2.05 2.18 2.32 2.20

Referring to Table 2, Examples 1 and 2 containing a clay mineral with respect to 100 parts by weight of butyl rubber can be seen that NBS wear resistance is two to three times higher than Comparative Example 1. In addition, Examples 3 and 4 in which the halogenated butyl rubber, styrene / butadiene rubber, and styrene block copolymers include clay minerals based on 100 parts by weight of the polymer substrate expressing the slow recovery characteristics have higher NBS wear resistance than Comparative Example 2. It can be seen that the improvement is 1.6 to 2 times.

In addition, Examples 1 and 2 it can be seen that the tear strength is improved by 10 to 16% compared to Comparative Example 1, Examples 3 and 4 it was confirmed that 19 to 35% improved compared to Comparative Example 2. In addition, it can be seen that the use of the reinforcing filler can be lowered according to the application of the clay mineral, so that the specific gravity is lowered and the weight can be reduced.

In addition, Examples 1 to 4 show very small values (11 to 13) in the resilience to distinguish the slow recovery characteristics of the polymer material, and it can be seen that copper slip maintains a very high level of 2.0 or more.

In addition, it can be seen that Examples 1 and 2 have improved the durability, significantly improved the wear resistance of the outsole for shoes expressing the slow recovery characteristics of the conventional butyl rubber alone, prepared in Examples 3 and 4 It can be seen that the shoe outsole specimen exhibits a level of physical property that can be used as a normal shoe outsole in terms of mechanical properties and abrasion resistance. That is, it can be seen that the shoe sole specimens prepared in Examples 1 to 4 can be used as shoe soles having an excellent anti-slip effect.

In addition, it was confirmed that similar characteristics as in Examples 1 to 4 were obtained for Examples 5 to 12.

Although the preferred embodiments of the present invention have 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 (17)

100 parts by weight of polymer material,
Clay minerals 0.1 to 20 parts by weight,
0.5 to 10 parts by weight of anionic surface modifier, and
0.05 to 60 parts by weight of a crosslinking agent,
The anionic surface modifier is any one selected from the group consisting of poly oxyethylene nonylphenyl ether, lauryl sampioi phosphoric acid, sodium dioctyl sulfosuccinate, sodium dialkyl sulfosuccinate, and combinations thereof Insole composition. The method of claim 1,
The clay mineral is any one selected from the group consisting of kaolinite, dekite, halosite, montmorillonite, bentonite, acid clay, illite, haeolite and combinations thereof. The method of claim 1,
The clay mineral is a shoe sole composition that the average particle diameter of 0.1 to 10um. The method of claim 1,
The clay mineral surface is any one selected from the group consisting of dimethyl dihydrogenated tallow quaternary ammonium, methyl dihydrogenated tallow ammonium, dimethyl hydrogenated tallow 2-ethylhexyl quaternary ammonium and combinations thereof The sole composition for treating. The method of claim 4, wherein
Wherein the clay mineral 50 to 150mEq / 100g (clay) surface treatment composition for the outsole. delete The method of claim 1,
The polymer material is a shoe sole composition comprising any one selected from the group consisting of styrene-based block copolymers, solution-polymerized styrene / butadiene rubber, butyl rubber, natural rubber and combinations thereof. The method of claim 7, wherein
The polymer material is a shoe sole comprising 20 to 40 parts by weight of a styrenic block copolymer, 10 to 30 parts by weight of solution-polymerized styrene / butadiene rubber, 30 to 50 parts by weight of halogenated butyl rubber and 0 to 20 parts by weight of natural rubber Composition. The method of claim 7, wherein
The styrene-based block copolymer is a shoe sole composition that is a double or triple block copolymer consisting of a hard block and a soft block. 10. The method of claim 9,
The hard block is polystyrene,
The soft block is any one selected from the group consisting of 3,4-polyisoprene, polybutadiene, hydrogenated 3,4-polyisoprene, hydrogenated polybutadiene and combinations thereof having a glass transition temperature of -20 to 30 ° C. That
Shoe outsole composition. The method of claim 7, wherein
The solution-polymerized styrene / butadiene rubber is a shoe sole composition that the glass transition temperature is -40 to 20 ℃. The method of claim 7, wherein
The butyl rubber is a copolymer of isobutylene and isoprene (isoprene), the degree of unsaturation is 0.6 to 2.5 mol% composition for outsole. The method of claim 7, wherein
The butyl rubber is any one halogenated butyl rubber selected from the group consisting of chlorinated-isobutylene-isoprene rubber, brominated-isobutylene-isoprene rubber and combinations thereof. The method of claim 1,
Wherein the cross-linking agent is any one selected from the group consisting of sulfur crosslinking agent, organic peroxide crosslinking agent, resin crosslinking agent and combinations thereof. The method of claim 1,
The shoe sole composition is a shoe sole composition further comprises any one of 3 to 100 parts by weight of a filler selected from the group consisting of silica, carbon black, calcium carbonate, talc and combinations thereof. The method of claim 1,
The shoe sole composition may be any one of rubber additives selected from the group consisting of a tackifier, an extended oil, an antioxidant, an ozonation inhibitor, a pigment, a silane coupling agent, a homogeneous compound, and a combination thereof. Shoe sole composition that is further comprising by weight. A shoe outsole manufactured by compression molding the composition for shoe insole according to claim 1 for 3 to 30 minutes at a molding temperature of 100 to 200 ° C. and a molding pressure of 100 to 300 kg / cm 2.