JP2002282006A - Outsole, and shoes equipped with the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an outsole for shoes, which displays a sufficient anti- slipping property even on the wet ground, and also, is excellent in water- resistance and chemical-resistance, and shoes equipped with the outsole. SOLUTION: This outsole 5 for a shoe 1 comprises a crosslinking molded body of a rubber composition. In this case, the base material polymer of the rubber composition contains a main polymer (a bromide of a copolymer of isobutylene and paramethylstyrene). The mass ratio of the main polymer based on the base material polymer is preferably 5% or higher. Preferably, carbon black of which the particulate diameter is from 10 nm to 60 nm is contained in the rubber composition. The blending amount for the carbon black is preferably from 10 parts to 65 parts based on 100 parts of the base material polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shoe outsole which is particularly suitable for shoes which often come into contact with a solution containing water, chemicals and the like, and a shoe provided with the outsole.

[0002]

2. Description of the Related Art Shoes, such as walking shoes and trekking shoes, have an outsole forming a bottom surface thereof. Usually, the outsole is formed from a polymer composition based on rubber or the like. An important performance required for the outsole is that it does not slip easily on the ground, that is, it has good slip resistance.

For the purpose of improving the anti-slip property, various measures have been conventionally taken on the outsole. For example, Japanese Patent No. 2957480 discloses an outsole having improved anti-slip properties by using a specific solution-polymerized styrene-butadiene rubber. Also, Japanese Patent Application Laid-Open No. 9-32
Japanese Patent No. 2807 discloses an outsole in which the slip resistance is enhanced by adding a clay and a silane coupling agent to a diene rubber.

[0004]

On the other hand, recently, water sports such as aquabics and walking in a pool have become popular, and for example, pool-specific shoes or the like corresponding to each sport have begun. However, an outsole having water resistance, chemical resistance and anti-slip property, particularly anti-slip property on wet ground (hereinafter referred to as "wet grip property"), which can be satisfied as the above-mentioned pool exclusive shoes, has been developed. Absent.

[0005] The present invention has been made in view of such circumstances, and exhibits sufficient anti-slip properties even on wet ground.
It is another object of the present invention to provide a shoe outsole excellent in water resistance and chemical resistance, and a shoe provided with the outsole.

[0006]

The present inventors conducted tests on various materials that can constitute the base polymer of the outsole, and as a result, found that a bromide of a copolymer of isobutylene and paramethylstyrene (hereinafter referred to as a bromide) was used. (Abbreviated as "this polymer")
Was found to have excellent wet grip properties and water and chemical resistance.

[0007] The invention for solving the above-mentioned problems obtained as a result is an outsole for shoes comprising a crosslinked molded article of a rubber composition, wherein the base polymer of the rubber composition contains the present polymer. It is characterized by the following.

Since the base polymer of the rubber composition as the molding material contains the present polymer, the outsole is excellent in anti-slip properties, particularly in wet grip properties, and also in water resistance and chemical resistance. Therefore, the outsole is often in contact with a solution containing chemicals such as water and chlorine, and is suitable for shoes that require sufficient anti-slip properties on wet ground (for example, the above-mentioned pool shoes). .

In the outsole, the mass ratio of the present polymer to the base polymer is preferably 5% or more. When the mass ratio of the present polymer to the base polymer of the rubber composition is 5% or more, the above wet grip properties and water / chemical resistance can be effectively exhibited.
Therefore, other polymers such as styrene-butadiene rubber and butadiene rubber can be included in the base polymer of the rubber composition, and cost reduction and other functionalities can be provided.

The rubber composition preferably contains carbon black having a particle diameter (average primary particle diameter) of 10 nm or more and 60 nm or less. Thus, the wear resistance of the outsole can be increased by including a relatively small diameter carbon black in the rubber composition.

The amount of the carbon black is preferably from 10 to 65 parts based on 100 parts of the base polymer. Here, the numerical value indicated by “part” means a ratio based on mass. By setting the blending amount of carbon black in the above range, the above-mentioned action of improving the wear resistance can be effectively exerted, and the workability in the production process of the outsole is also improved.

[0012] Accordingly, the shoe using the outsole has a remarkably excellent gripping property, and is less likely to slip particularly on wet ground. In addition, water (particularly a solution containing chemicals such as chlorine) for excellent water resistance and chemical resistance
It can be used even in an environment where it is in contact with water, and is suitable for, for example, water sports shoes such as pool-dedicated shoes, and safety shoes for work sites such as chemical manufacturing.

[0013]

Embodiments of the present invention will be described below in detail with reference to the drawings as appropriate. FIG. 1 is a partially broken side view showing a shoe according to an embodiment of the present invention.

A shoe 1 shown in FIG. 1 is a general athletic shoe, and includes an upper portion 2, an insole 3, a midsole 4 and an outsole 5. The insole 3, the midsole 4 and the outsole 5 constitute a sole portion (shoe sole). The midsole 4 and the insole 3 are not provided depending on the use of the shoe 1 among the respective parts constituting the sole part. The material, shape, and the like of the upper portion 2 are appropriately changed according to the use of the shoe 1 or the like.

The outsole 5 is a flat plate-like body that matches the sole of the foot, and has a shape that is inverted left and right by the right and left shoes 1. The outsole 5 is formed by crosslinking and molding a rubber composition. The base polymer of the rubber composition contains the present polymer. By including the present polymer, the wet grip properties of the outsole 5 are enhanced, and the water resistance and chemical resistance are also enhanced.

This polymer is obtained by copolymerizing isobutylene represented by the following chemical formula (1) and paramethylstyrene represented by the following chemical formula (2), and the obtained copolymer is brominated with, for example, bromine (Br). It is manufactured by. As a specific example of the present polymer, a product name “EXPRO” manufactured by Exxon Chemical Co., Ltd.
90-10, Explore 89-4 "and the like.

[0017]

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[0018]

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In the present polymer, it is considered that halogen such as bromine mainly replaces hydrogen of a methyl group substituted at the p-position of the phenyl group of the styrene portion in the copolymer. The various attributes of the polymer are not particularly limited, but the copolymerization ratio of isobutylene and paramethylstyrene is preferably about 99: 1 to 85:15 by mass ratio, and the halogen content such as bromine is 0.3 to
About 2.0% by mass is preferable.

The mass ratio of the present polymer to the base polymer is preferably at least 5%, particularly preferably at least 10%, more preferably at least 15%, even more preferably at least 50%.
% Or more is most preferable. By setting the mass ratio of the present polymer in the above range, the effect of improving the wet grip properties and water / chemical resistance of the outsole can be effectively exhibited. Therefore, it is possible to blend a polymer other than the present polymer into the base polymer from the viewpoints of reducing material costs, improving strength, improving wear resistance, improving workability, and the like.

Other rubbers blended in the base polymer include, for example, natural rubber, acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (SB)
R), butadiene rubber (BR), isoprene rubber (I
R), butyl rubber (IIR), chloroprene rubber (C
R), ethylene-propylene-diene rubber (EPD)
M), ethylene-propylene rubber (EPM), acrylic rubber, epichlorohydrin rubber, polysulfide rubber, urethane rubber and the like. It is also possible to mix a synthetic resin, a thermoplastic elastomer, or the like. However, other polymers to be blended include chlorinated butyl rubber, high molecular weight polyisobutylene, butadiene rubber, chloroprene rubber, and natural rubber which have compatibility with the above-mentioned polymer and can form a good co-vulcanized product. Rubber is preferred.

The above rubber composition is crosslinked by known means, and can be vulcanized by a combination system of a vulcanizing agent and a vulcanization accelerator as in the prior art. As the vulcanizing agent, sulfur is used, and N, N'-diphenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-
Amines such as phenyl-p-phenylenediamine or resins such as an alkylphenol formaldehyde resin can also be used.

Examples of the vulcanization accelerator include thiazoles such as 2-mercaptobenzothiazole and dibenzothiazyl disulfide; and thiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide and dipentamethylenethiuram tetrasulfide. Vulcanization accelerators: iron dimethyldithiocarbamate, zinc dimethyldithiocarbamate,
Dithiocarbamic acids such as copper dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate and zinc ethylphenyldithiocarbamate are used.

[0024] In addition, a vulcanization accelerating aid such as zinc oxide and stearic acid may be used in combination with the above combination system as in the prior art.
In the combined system, the total amount of the vulcanizing agent and the vulcanization accelerator, or the total amount of the vulcanizing agent, the vulcanization accelerator and the vulcanization accelerator, based on 100 parts of the base polymer, One to 20 parts is preferable.

The above rubber composition can be vulcanized only with zinc oxide and stearic acid, which are vulcanization accelerating aids, and the above vulcanization accelerator may be used in combination with this system. The amount of the zinc oxide to be added is 0.1 to 100 parts of the base polymer.
1 part or more and 15 parts or less are preferable, and 1 part or more and 5 parts or less are more preferable. The blending amount of stearic acid is preferably 0.1 part or more and 20 parts or less, more preferably 0.5 part or more and 3 parts or less based on 100 parts of the base polymer.

For the purpose of improving the strength, a filler is preferably compounded in the rubber composition. As the filler used,
Examples include carbon black, silica, calcium carbonate, clay and the like. Among them, carbon black having a relatively small diameter which is excellent in a reinforcing effect, particularly in improving abrasion resistance, is preferred.

The lower limit of the particle size of the carbon black is preferably 10 nm, and particularly preferably 19 nm. On the other hand, the upper limit of the particle diameter of carbon black is 60 n
m, particularly preferably 57 nm, more preferably 32 nm. When the particle size of the carbon black is in the above range, the effect of improving the abrasion resistance can be effectively exerted, and the workability in the process of manufacturing the outsole is also improved.

Specific examples of suitable carbon black include Super Abr having a particle diameter of 11 nm to 19 nm as measured according to "ASTM D1765".
asion furance (SAF), particle diameter 2
Intermediate from 0 nm to 25 nm
Super Abrasion Furnace (IS
AF), Hig with a particle diameter of 26 nm to 30 nm
h AbrasionFurnace (HAF) and the like.

It is to be noted that silica, calcium carbonate, carbon black having a particle diameter of more than 60 nm, etc. may be used in combination with the above-mentioned small carbon black having a particle diameter of 10 to 60 nm.

The lower limit of the amount of the carbon black is 10 parts, especially 20 parts, per 100 parts of the base polymer.
Parts, more preferably 30 parts. On the other hand, the upper limit of the amount of the carbon black is preferably 65 parts, particularly preferably 60 parts. This is because if the amount of carbon black is less than the above lower limit, the effect of improving the abrasion resistance of the outsole 5 is small. This is because the rubber may be burned due to excessive rise.

Further, additives such as a plasticizer, an antioxidant and a coloring agent may be appropriately compounded in the rubber composition. When silica is used as the filler, a suitable amount of a silylating agent or a silane coupling agent may be added together with silica, whereby the water repellency of the outsole 5 is improved.

The method of manufacturing the outsole 5 is as follows.
(A) a step of kneading a base polymer, a crosslinking agent, various additives, and the like with, for example, an internal mixer (for example, a Banbury mixer or a kneader) or an open roll to obtain a rubber composition; (C) charging the product into a mold having a cavity having the same shape as the outsole 5;
The step of heating and pressurizing the rubber composition to cause a cross-linking reaction is a main step, and the outsole 5 is formed through these steps. Of course, another molding method such as an injection molding method may be used. The rubber composition of the present invention is preferably kneaded with a Banbury mixer and press-vulcanized.

The shoe 1 is manufactured by joining the upper part 2, the insole 3, the midsole 4 and the outsole 5 by known means. The shoe 1 provided with the outsole 5 includes a shoe, which is often used on wet ground, particularly a chemical such as chlorine, because the outsole 5 has excellent wet grip properties and water and chemical resistance as described above. It is suitable for shoes used in an environment where the solution to be used is present.
Specifically, pool exclusive shoes, deck shoes, bath shoes, rain shoes, fishing boots,
It is suitable for diving shoes, flip flops, safety shoes, trekking shoes, walking shoes, golf shoes, motorcycle shoes, and the like.

[0034]

EXAMPLES Hereinafter, the effects of the present invention will be clarified by examples, but the present invention should not be construed as being limited based on the description of the examples.

(Experiment 1) [Example 1] 100 parts of the present polymer (trade name “EXPRO 90-10” of Exxon Chemical Co.) as a base polymer,
Carbon black having a particle size of 23 nm as a filler (1) (trade name “Diablack I” of Mitsubishi Kasei Co., Ltd.) 4
5 parts, 2.0 parts of process oil (trade name "PW380" of Idemitsu Kosan Co., Ltd.) as a softener, 2,2 of antioxidant (1)
6-di-tert-butyl-4-methylphenol (trade name “Nocrack 200” of Ouchi Shinko Chemical Co., Ltd.)
0 parts, another anti-aging agent (2) (trade name “Sunnock N” of Ouchi Shinko Chemical Co., Ltd.) 0.5 part, sulfur 1.0 part, dibenzothiazyl disulfide of vulcanization accelerator (1) ( Ouchi Shinko Kagaku Kogyo Co., Ltd. product name “Noxeller DM”) 2.0 copies,
Blend 2.0 parts of zinc oxide and 1.0 part of stearic acid,
A rubber composition was obtained by kneading with a Banbury mixer, and this rubber composition was put into a mold for an outsole, and heated and pressed at 160 ° C. for 10 minutes to obtain an outsole of Example 1.

Example 2 As a base polymer, 90 parts of the present polymer and BR (trade name "BR1" of Nippon Synthetic Rubber Co., Ltd.)
1)), and the outsole of Example 2 was obtained in the same manner as in Example 1 above.

Example 3 An outsole of Example 3 was obtained in the same manner as in Example 1 except that 50 parts of the present polymer and 50 parts of the above BR were blended as the base polymer.

Example 4 An outsole of Example 4 was obtained in the same manner as in Example 1 except that 15 parts of the present polymer and 85 parts of BR were blended as base polymers.

Example 5 An outsole of Example 5 was obtained in the same manner as in Example 1 except that 10 parts of the present polymer and 90 parts of BR were blended as base polymers.

Example 6 An outsole of Example 6 was obtained in the same manner as in Example 1 except that 3 parts of the present polymer and 97 parts of BR were blended as base polymers.

Example 7 In place of the above carbon black, 45 parts of silica (1) (trade name “Ultrasil VN3” of Degussa) was blended as a filler, and bis- (3- (3-) was used as a silane coupling agent. Triethoxysilylpropyl) tetrasulfen (trade name “Si6
9)) An outsole of Example 7 was obtained in the same manner as in Example 1 except that 4.0 parts were blended.

Example 8 As in Example 7, except that 45 parts of the above silica (1) was blended as a filler and 4.0 parts of the above silane coupling agent were further blended. Thus, an outsole of Example 8 was obtained.

Example 9 Similar to Example 7, except that 45 parts of the above-mentioned silica (1) was blended as a filler and 4.0 parts of the above-mentioned silane coupling agent was further blended. Thus, an outsole of Example 9 was obtained.

Example 10 In the same manner as in Example 7, except that 45 parts of the above-mentioned silica (1) was blended as a filler and further 4.0 parts of the above-mentioned silane coupling agent was blended. Thus, an outsole of Example 10 was obtained.

Comparative Example 1 The above BR was used as a base polymer.
An outsole of Comparative Example 1 was obtained in the same manner as in Example 1 except that 100 parts were blended.

Comparative Example 2 NBR as a base polymer
(Product name "ZIPOL DN200" of Zeon Corporation)
An outsole of Comparative Example 2 was obtained in the same manner as in Example 1 except that 00 parts were blended.

Comparative Example 3 The above BR was used as a base polymer.
25 parts, 75 parts of solution-polymerized styrene-butadiene rubber (trade name "Nippol NS116" of Nippon Zeon Co., Ltd.) and 60 parts of silica (2) (trade name "Nip Seal VN3" of Nippon Silica Co., Ltd.) as a filler are further compounded. 6.0 parts of the above-mentioned silane coupling agent was added, the compounding amount of the softener was 5.0 parts, the compounding amount of sulfur was 2.0 parts, the compounding amount of zinc oxide was 3.0 parts, and the antioxidant ( 2) N-te of vulcanization accelerator (2) was added without adding vulcanization accelerator (1).
rt-butyl-2-benzothiazolylsulfenamide (trade name "Noxeller NS" of Ouchi Shinko Chemical Co., Ltd.)
An outsole of Comparative Example 3 was obtained in the same manner as in Example 1 except that 1.5 parts was compounded.

Comparative Example 4 The above BR was used as a base polymer.
30 parts, 70 parts of natural rubber (NR), 50 parts of carbon black (4) having a particle size of 57 nm as a filler (trade name of "Niteron # 55U" of Nippon Steel Chemical Co., Ltd.) and clay (trade name of Shiraishi Calcium Co., Ltd.) 30 parts of "No. 80" (clay composed mainly of kaolinite)), 3.0 parts of the above silane coupling agent, 1.0 part of antioxidant (1), sulfur And 2.0 parts of zinc oxide and 3.0 parts of zinc oxide without the softener and antioxidant (2), and the vulcanization accelerator (1) instead of the vulcanization accelerator (1). An outsole of Comparative Example 4 was obtained in the same manner as in Example 1 except that 1.5 parts of the accelerator (2) was blended.

[Evaluation of Characteristics] The outsole of Examples 1 to 10 and the outsole of Comparative Examples 1 to 4 were subjected to a wet grip test and a water / chemical resistance test to be described later. -The chemical resistance was evaluated. The results are shown in Table 1 below.

[Wet grip test] A shoe was manufactured by joining the separately manufactured upper to the outsole, and ten testers put on the shoe and performed an anti-slip feeling test in the pool.
The points were evaluated at least 1 point, and the evaluation values by 10 testers were averaged.

[Water resistance / chemical resistance test] Outsole 1
0 pieces were immersed in water containing chloride ions in the pool, left for one month, taken out, visually observed for abnormalities such as cracks and slime, and evaluated according to the following criteria. The evaluation criteria are as follows: Out of 10 outsole, no abnormality is found in all, out of 2 to 5 outsole is anomaly, and out of 6 to 9 outsole is inferior. And the case where all of them were abnormal was evaluated as x.

[0052]

[Table 1]

From Table 1 above, it can be seen that the outsoles of Examples 1 to 10 are superior to the outsoles of Comparative Examples 1 to 4 in both wet grip properties and water / chemical resistance. On the other hand, the outsoles of Comparative Examples 1, 3, and 4 using BR, SBR or NR as the base polymer lack particularly wet grip properties, and the outsoles of Comparative Example 2 using NBR as the base polymer have high wet grip properties. However, it is inferior in water resistance and chemical resistance. From the evaluation results, the superiority of the present invention is apparent. When the outsole of Examples 1 to 4 using carbon black as a filler and the outsole of Examples 7 to 10 using silica were compared, the wet grip property and the water resistance were obtained using either filler.・ Excellent in chemical resistance.

(Experiment 2) [Example 11] Same as Example 1 except that 40 parts of carbon black (2) having a particle diameter of 19 nm (trade name "Diablack A" of Mitsubishi Kasei Co., Ltd.) was blended as a filler. Thus, an outsole of Example 11 was obtained.

Example 12 An outsole of Example 12 was obtained in the same manner as in Example 1 except that 20 parts of the above carbon black (2) was blended as a filler.

Example 13 A filler having a particle diameter of 32 was used.
Example 1 except that carbon black (3) (trade name “Diablack HA” of Mitsubishi Kasei Co., Ltd.) was used.
In the same manner as in the above, an outsole of Example 13 was obtained.

Example 14 An outsole of Example 14 was obtained in the same manner as in Example 1 except that 60 parts of the above carbon black (4) was blended as a filler.

Example 15 Example 1 was repeated in the same manner as in Example 1 except that 30 parts of carbon black (1) and 20 parts of the above carbon black (4) were blended as fillers.
5 outsole were obtained.

Example 16 An outsole of Example 16 was obtained in the same manner as in Example 1 except that 10 parts of the above silica (1) was further added as a filler in addition to carbon black (1).

[Example 17] In addition to carbon black (1), carbon black (5) having a particle diameter of 72 nm as a filler (trade name "Niteron # 7" from Nippon Steel Chemical Co., Ltd.)
5 ") An outsole of Example 17 was obtained in the same manner as in Example 1 except that 10 parts were compounded.

Example 18 An outsole of Example 18 was obtained in the same manner as in Example 1 except that the blending amount of carbon black (1) was changed to 70 parts.

Example 19 An outsole of Example 19 was obtained in the same manner as in Example 1 except that the carbon black (5) was used instead of the carbon black (1).

[Evaluation of Characteristics] The above Examples 1, 5 to 7, 1
Using the outsoles of Nos. 1 to 19 and the outsoles of Comparative Examples 3 and 4, the above-mentioned wet grip property test and the abrasion resistance test and workability test to be described later were performed. The workability and workability were evaluated. The results are shown in Table 2 below.

[Abrasion Resistance Test] A disk-shaped test piece having a thickness of 12.7 mm was prepared under the same molding conditions as the above outsole, and the Akron abrasion test in accordance with JIS-K-6264 was performed using this test piece. Was performed, and the wear capacity was measured, and the wear resistance of each outsole was evaluated from the wear capacity.

[Workability test] In the production process of each of the above outsoles, 場合 indicates that the rubber composition after kneading with the Banbury mixer has not burnt rubber, Δ indicates that the rubber composition has slightly burnt rubber, Was evaluated as x when the occurrence of the phenomenon occurred.

[0066]

[Table 2]

From Table 2 above, the outsoles of Comparative Examples 3 and 4 using BR, SBR or NR as the base polymer are inferior in wet grip properties. On the other hand, it can be seen that the outsoles of Examples 1, 5 to 7, and 11 to 19, which include the present polymer as the base polymer, have both high wet grip properties, abrasion resistance and workability. From the evaluation results, the superiority of the present invention is apparent. In Examples, the outsole of Example 19 using carbon black (5) having a particle diameter of more than 60 nm as a filler and the outsole of Example 7 using silica (1) had a particle diameter of more than 60 nm. 60nm or less carbon black (1)
The outsole of the other examples incorporating (4) is superior in abrasion resistance. In addition, the compounding amount of the filler is 65
In comparison with the outsole of Example 18 in which the amount exceeds 65 parts, the other outsole having a compounding amount of 65 parts or less has better workability.

[0068]

As described above, according to the outsole of the present invention, both the wet grip property, the water resistance and the chemical resistance are superior to the conventional outsole, and the abrasion resistance and workability are improved. Is also excellent. The shoe provided with this outsole has a low occurrence of cracks and other abnormalities even in an environment where a solution containing a chemical such as water or chlorine is present, and is unlikely to cause slippage. Therefore, these shoes are suitable for aquabics, pool-dedicated shoes for walking in a pool, etc., which have become popular today.

[Brief description of the drawings]

FIG. 1 is a partially broken side view showing a shoe according to an embodiment of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Shoes 2 ... Upper part 3 ... Insole 4 ... Midsole 5 ... Outsole

Claims (5)

[Claims] 1. A shoe outsole comprising a crosslinked molded article of a rubber composition, wherein the base polymer of the rubber composition contains a bromide of a copolymer of isobutylene and paramethylstyrene. Outsole to feature. 2. The outsole according to claim 1, wherein the mass ratio of the bromide of the copolymer of isobutylene and paramethylstyrene to the base polymer is 5% or more. 3. The rubber composition according to claim 1, wherein the rubber composition has a thickness of 10 nm to 60 nm.
A carbon black having the following particle size:
Or the outsole according to claim 2. 4. The outsole according to claim 3, wherein the compounding amount of the carbon black is 10 parts or more and 65 parts or less based on 100 parts of the base polymer. 5. A shoe provided with the outsole according to any one of claims 1 to 4.