JPH1160751A - Non-slipping material, footwear sole by using the same, and production of slide-preventing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a non-slipping material, having excellent slip-preventing properties on a slippery surface such as an ice and snow surface without scratching a normal road surface, floor surface or the like by using a dienic rubber foam including dispersed particles containing norbornene. SOLUTION: This non-slipping material comprises a dienic rubber foam (constituted of a natural rubber, butadiene rubber and styrene/butadiene rubber with a low styrene content, and having 40-100% foaming rate) including particles containing a norbornene rubber (preferably having >=90 deg. hardness at 0 deg.C, 15-5 deg.C glass transition temperature and 0.1-3 mm particle diameter), dispersed in the foam. The slide-preventing material is obtained by compounding the particles containing the norbornene rubber, the dienic rubber component, a foaming agent, a vulcanizing agent and optionally other components, and vulcanizing the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-slip material having excellent anti-slip performance on a smooth surface such as an icy and snowy road surface or a road surface wet with water, and a shoe sole using the same. The present invention also provides a method for producing the anti-slip material.

[0002]

2. Description of the Related Art When walking on a pressed snow surface or an ice barn,
In order to prevent slipping, that is, to provide anti-slip properties, shoes in which a spike pin made of metal or polynorbornene that cures at low temperature is mounted on shoe soles have been developed and put into practical use. However, shoes with metal spiked pins have the problem of damaging the floor, and shoes with polynorbornen spiked pins, for example, in places like floors wet with water at room temperature. On the contrary, there is a problem that it is slippery.

[0003] Other shoes provided with anti-slip properties include:
It is also known that sand, gold steel sand, carborundum, glass, or other particulate matter is mixed into shoe soles, but these shoe soles have not been able to solve the above-mentioned problems.

[0004]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and has excellent anti-slip properties on smooth surfaces such as ice and snow surfaces and surfaces wet with water. An object of the present invention is to provide an anti-slip material that can be applied to all applications requiring anti-slip properties without damaging a floor or the like.

Another object of the present invention is to provide footwear soles, such as shoes, sandals, sandals, and clogs, using the anti-slip material.

[0006]

Means for Solving the Problems The present inventors have focused on the following points as a result of intensive studies to achieve the above object. That is, foamed rubber has better slip resistance on ice and snow surfaces than mere solid rubber, flexibility of rubber at low temperature is better than foamed rubber than solid rubber, and low glass transition temperature. The rubber containing a large amount of the rubber component has a higher coefficient of friction on ice and snow surfaces in both solid rubber and foamed rubber.

Further, the present inventors have conducted studies based on these points of interest, and as a result, have found a combination of a diene rubber and a norbornene rubber and an optimum combination method thereof, and have completed the present invention. Was.

[0008] In order to achieve the above object, the present invention provides a diene rubber foam as a matrix, in which particles containing norbornene rubber are dispersed and contained. Provide a conductive material.

Further, in order to achieve the above object, the present invention has a second aspect in which the diene rubber foam as a matrix has a foaming ratio of 40 to 100%.
An anti-slip material according to the preceding claims.

[0010] In order to achieve the above object, the present invention provides a third aspect of the present invention in which the particles containing norbornene rubber are used.
The anti-slip material according to claim 1, wherein the hardness at 0 ° C according to IS K6253-A is 90 degrees or more.

According to a fourth aspect of the present invention, there is provided the anti-slip material according to the first aspect, wherein the glass transition point of the particles containing norbornene rubber is in the range of 15 ° C. to 5 ° C. provide.

In order to achieve the above object, the present invention provides, as a fifth aspect, an anti-slip material according to the first aspect, wherein the particles containing norbornene rubber have a particle size of 0.1 to 3 mm.

According to a sixth aspect of the present invention, there is provided a shoe sole comprising the anti-slip material according to any one of the first to fifth aspects. .

In order to achieve the above object, the present invention provides, in a seventh aspect, a compound comprising a norbornene rubber component, a vulcanizing agent and other components as necessary, vulcanized, and then crushed to obtain a norbornene rubber component. A first step of producing particles containing bounene rubber, particles containing norbornene rubber, a diene rubber component,
A method for producing an anti-slip material, comprising a second step of blending a foaming agent, a vulcanizing agent, and other components as necessary, and vulcanizing the compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The anti-slip material of the present invention has a so-called sea-island structure, and contains particles containing norbornene rubber in a diene rubber foam (corresponding to the sea) serving as a matrix. (Corresponding to islands) are dispersedly included. The diene rubber foam contains closed cells dispersed in the same manner as particles containing norbornene rubber.

The rubber constituting the diene rubber foam as the matrix may be one or more selected from natural rubber, butadiene rubber, styrene / butadiene rubber having a low styrene content, and the like. In addition, a styrene / butadiene rubber having a relatively high glass transition point and a high styrene content can be blended in an amount that does not excessively increase the glass transition point of the rubber component.

Further, the foaming rate of the diene rubber foam is such that the flexibility of the foam at low temperature is ensured, and the bonding strength with the particles containing norbornene rubber is increased.
To increase the spike effect when using sole material,
-100%, preferably 50-7%.
It is preferably 0%. Note that the term "spike effect" as used herein means that when the anti-slip material of the present invention is used as a shoe sole material, the same anti-slip effect as the spike pin described in the section of the prior art is used.
Hereinafter, the same meaning is used. The foaming rate is
It is obtained from the following equation.

The foaming ratio (%) = {(the density of the rubber solid phase portion of the foamed rubber (g / cm ³⁾ - the density of the foamed rubber (g / cm ³⁾⁾ / foamed density of the rubber (g / cm ^3)} × 100

The particles containing norbornene rubber contained in the anti-slip material have a hardness at 0 ° C. of 90 ° or more according to JIS K6253-A. When the hardness is 90 degrees or more, the spike effect can be sufficiently exerted even on ice and snow near 0 ° C., for example.

The particles containing norbornene rubber can have a glass transition point in the range of room temperature to −50 ° C., preferably in the range of 15 ° C. to 5 ° C., and set the glass transition point in this range. When it is set so as to exhibit a flexible rubber elasticity at room temperature, it is rapidly cured from around 15 ° C. to 5 ° C., and exhibits an excellent spike effect as the temperature decreases.

The particle size of the particles containing norbornene rubber is preferably from 0.1 to 3 mm, particularly preferably from 0.5 to 2 mm in order to impart excellent anti-slip properties. The method for producing a non-slip material according to the present invention is a method for producing particles containing norbornene rubber by blending a norbornene rubber component, a vulcanizing agent and other components as necessary, vulcanizing and then crushing to produce particles containing norbornene rubber. And a second step of compounding and vulcanizing particles containing norbornene rubber, a diene rubber component, a foaming agent, a vulcanizing agent and other components as required. This manufacturing method can be applied as it is to a method of manufacturing a shoe sole.

First, the first step of the method for producing particles containing norbornene rubber will be described. Particles containing norbornene rubber, after mixing norbornene rubber component, process oil and vulcanizing agent, and other components as necessary, in the same manner as a general rubber manufacturing method, after molding vulcanization, It can be obtained by crushing with a crusher or the like.

The process oil is a hydrocarbon oil which is added to improve the processability of the rubber in ordinary rubber production. In the present invention, the glass transition point of the norbornene rubber is in the range of room temperature to -50 ° C. Within, preferably 15 ° C ~
It is added to adjust to a desired region within the range of 5 ° C. The amount added depends on the type of process oil and the glass transition point. For example, when the glass transition point of norbornene rubber is set to around 15 ° C. to 5 ° C., about 30 to 50 parts by weight of an aromatic process oil is blended with respect to 100 parts by weight of norbornene rubber.

Other components include a rubber reinforcing agent for improving the abrasion resistance and chipping resistance of norbornene rubber and for improving the rigidity associated with the increase in hardness at low temperatures to exert an excellent spike effect. Carbon black, white carbon and the like can be blended. In addition, known rubber additives such as an antioxidant, a vulcanization accelerator, a colorant, and a filler can be blended.

Next, a description will be given of the second step of the method for producing the anti-slip material. Anti-slip material is a diene rubber component, particles containing norbornene rubber, a foaming agent and a vulcanizing agent,
Further, if necessary, other known rubber additive components may be blended, followed by molding and vulcanization in the same manner as in a general rubber production method.

The mixing ratio of the particles containing the diene rubber component and the norbornene rubber is such that an excellent spike effect is imparted, the flexibility of the diene rubber serving as the matrix at low temperatures is increased, and the slip resistance is enhanced. System rubber component 10
5 to 4 parts by weight of particles containing norbornene rubber per 0 parts by weight.
It is preferable to mix 0 parts by weight, particularly preferably 10 to 30 parts by weight.

As a foaming agent, azodicarbonamide, N, N'-dinitrosopentamethylenetetramine, 4,4 'to obtain a foam containing uniform closed cells and fine cells.
-Oxybis (benzenesulfohydrazide), p-toluylenesulfonyl semicarbazide and the like can be used.

In the method for producing an anti-slip material according to the present invention, a step of buffing the surface of the obtained anti-slip material can be added if necessary. By this buffing, a diene rubber foam portion serving as a matrix is scraped off, and particles containing norbornene rubber are projected to the surface. By this treatment, the spike effect is further improved by the action of the particles containing the protruding norbornene rubber.

In the present invention, the following excellent effects can be imparted to the anti-slip material by applying such a two-stage manufacturing method.

(1) A diene rubber serving as a matrix is a uniform foam having closed cells, in which particles containing norbornene rubber are uniformly dispersed (having a sea-island structure) in a desired shape. An anti-slip material can be obtained.

On the other hand, when the rubber composition is produced in one step, that is, when the diene rubber component and the norbornene rubber component are mixed and molded and vulcanized, the mixture between the diene rubber phase and the norbornene rubber phase is reduced. Since the foaming state becomes non-uniform, it is not possible to stably obtain a slip resistant material having a desired shape.

(2) By forming a sea-island structure, an excellent spike effect can be exerted at a low temperature due to the interaction between a flexible diene rubber and particles containing hard norbornene rubber. On the other hand, in the case of manufacturing in one step, the sea-island structure cannot be formed, so that the spike effect is not exhibited.

(3) Since particles containing norbornene rubber are produced independently, it is easy to increase the strength of the particles by adding a reinforcing agent. For this reason, the hardness difference between the particles containing norbornene rubber and the diene rubber phase can be increased, so that the spike effect can be further enhanced. On the other hand, when it is manufactured in one step, the reinforcing agent acts so as to impair the flexibility of the diene rubber phase at low temperatures.

(4) At the time of the second-stage vulcanization reaction, the surface layers of the particles containing the diene rubber and the norbornene rubber are co-vulcanized and bonded, so that both rubbers are strongly bonded,
Be integrated. For this reason, particles containing norbornene rubber hardly fall off from the anti-slip material.

The anti-slip material of the present invention has excellent anti-slip properties due to such an action, but at the same time, as other effects naturally obtained from its structure,
It also has soundproofing, shock absorbing and heat insulating properties.

Next, a shoe sole using such an anti-slip material will be described. The footwear sole of the present invention is obtained by processing the slip resistant material into a desired shape. As described above, in the second step of the method for producing the slip resistant material, the footwear sole is directly formed into the desired shape of the shoe sole. A molding vulcanization method is also applicable.

The footwear sole of the present invention is particularly suitable as, but not limited to, a shoe footwear that is worn on extremely slippery places such as ice and snow surfaces or ice burns. In addition, shoes used in places where the floor is always wet and slippery, such as cooking areas and fishery processing areas, rain boots, as well as shoes used on ordinary road surfaces, sandals, sandals , Clogs, etc., and can also be used for indoor shoes such as slippers. Further, if the above-described soundproofing property, shock absorbing property and heat insulating property are utilized, it is possible to further add a new function to the above various types of footwear soles.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 Particles containing norbornene rubber were first produced by the following first-stage production method using the components having the compositions shown in Table 1.

[0040]

(Table 1) (Ingredients) (parts by weight) Polynorbornene 100 (trade name: Nosorex: Zeon Corporation) Aromatic process oil 40 White carbon 40 Stearic acid 1 Antioxidant 1 Zinc white 5 Vulcanization acceleration Agent 5 Sulfur 2

(Production method) Each component was mixed, and the mixture was pressure-vulcanized at 160 ° C for 10 minutes in a mold to obtain a rubber molded body. This rubber molded product was pulverized by a pulverizer to obtain particles containing norbornene rubber having a particle size of 0.1 to 3 mm. JIS K62 of particles containing this norbornene rubber
FIG. 1 shows the relationship between temperature and hardness according to 53-A. As is clear from FIG. 1, the hardness at around 0 ° C. (that is, corresponding to the ice and snow surface) was 90 degrees or more. Further, the hardness rapidly increased from around 15 ° C., which is the glass transition point, as the temperature decreased.

Next, using the components having the composition shown in Table 2, a shoe sole made of an anti-slip material was manufactured by the following second-stage manufacturing method.

[0043]

[Table 2] (Ingredient) (parts by weight) Styrene / butadiene rubber (23.5 / 76.5) 70 polybutadiene rubber 30 white carbon 35 process oil 5 process resin 5 stearic acid 1 zinc white 5 antioxidant 1 vulcanization accelerator 1 sulfur REFERENCE SIGNS LIST 1 foaming agent N, N'-dinitrosopentamethylenetetramine 2 urea 2 particles containing norbornene rubber 15

(Production method) Each component was mixed, filled in a shoe sole mold, and foamed and vulcanized while being pressed at 160 ° C. for 8 minutes to obtain a shoe sole as shown in FIG. The foaming ratio of the diene rubber foam was 57%. FIG. 1 shows the relationship between the temperature and the hardness of the diene rubber foam portion in the anti-slip material constituting the sole. The hardness is JIS K625.
The results of measurement by both 3-A and sponge hardness meter type C (manufactured by Kobunshi Keiki) are shown. As is clear from FIG.
The hardness around 0 ° C (that is, corresponding to the ice surface)
The order was 50 degrees or less and 70 degrees or less, which was considerably softer than particles containing norbornene rubber.
Also, the increase in hardness due to the decrease in temperature was slow. From the results shown in FIG. 1, it was confirmed that the particles containing norbornene rubber were hardened by the decrease in temperature, but the diene rubber foam still maintained flexibility.

Further, as shown in FIG. 3, the cross section of the shoe sole is such that particles containing norbornene rubber and closed cells are dispersed and contained in a diene rubber serving as a matrix. Therefore, the particles containing the soft diene rubber and the hard norbornene rubber can be grounded to the road surface in the same state.

The shoe sole may have a two-layer structure, as shown in FIG. This shows the ground plane
And a foot-side surface formed of another material, for example, only a diene-based foam.

Test Example 1 An anti-slip material (product of the present invention) obtained by the same composition and method as in Example 1 and the same procedure as in Example 1 except that particles containing norbornene rubber in Table 2 were excluded. The anti-slip property on ice was tested by the following method using the obtained comparative product.

(Test Method) First, a test plate (10 × 50 × 50 mm) made of the product of the present invention and the comparative product was prepared. Next, the test plate was placed in a container covered with a heat insulating material at -20 ° C.
The sample was placed on an ice block having a horizontal smooth surface and allowed to stand, and a load of 5 kg was applied to the test plate. Then, the stress (friction stress) when the test plate was pulled at a speed of 50 mm / min in the horizontal direction with respect to the ice surface was measured. FIG. 5 shows the results. The chart speed of the graph shown in FIG. 5 is 50 mm / min.

The graph of FIG. 5 (a) shows how the test plate (the product of the present invention) stops when it slides on ice and stops and then slides. That is, the maximum stress (static friction force) is shown in the initial stage of tension (point A), and the stress (dynamic friction stress) rapidly decreases when slipping starts, but when the stress decreases to a certain level (point B), the stress increases again. (Point C) indicates that this is repeated. The friction stress at each point was 2.9 kgf at point A, 1.7 kgf at point B, and 2.8 kgf at point C.
It was 3 kgf. When the friction coefficient was determined from these friction stresses, they were 0.58, 0.34, and 0.46, respectively.

FIG. 5B is a graph showing a test plate (comparative product).
Indicates the same state as the product of the present invention. The friction stress of each of the points A 'was 2.6 kgf and B'
The point was 1.1 kgf and the point C 'was 2.4 kgf. Also,
Each friction coefficient is 0.52, 0.22, 0.48
Met.

As is clear from the comparison between FIGS. 5A and 5B, the difference between the product of the present invention and the comparative product is that the product of the present invention is superior in static stress and the lower limit at which the dynamic friction stress decreases. The value of the product of the present invention was higher. Another difference was that the product of the present invention had a smaller upper and lower period width of stress. These differences indicate that the product of the present invention has better anti-slip properties than the comparative product.

Test Example 2 The shoe sole of the present invention (of Example 1) and the shoe sole of the comparative example (having the same composition as the comparative product of Test Example 1 and having the sole shape of Example 1)
Were manufactured using the same method as described above, and an actual wear test was conducted using 10 panels each.

In the actual wear test, the user walked on an ice barn at −2 to −5 ° C., and tested the slippage at the time of landing, the stepping weight shift and the slipping state at the time of kicking. As a result, 10
The panel using the shoe sole of the present invention was evaluated as being less slippery and easier to walk. In a place where the ice burn was wet, the shoe sole of the present invention was evaluated to be particularly easy to walk without slipping. In addition,
I walked on the plastic floor with my shoes on,
The floor surface was not damaged when the shoe sole was rubbed as well as when walking normally. In addition, there was no particular sound when walking indoors as in the case of ordinary athletic shoes.

[0054]

The slip-resistant material of the present invention and the shoe sole using the same have an interaction between a diene rubber foam portion having flexibility even at low temperatures and particles containing norbornene rubber having high hardness at low temperatures. Therefore, it has excellent anti-slip properties even in very slippery places such as ice and snow surfaces. In addition, particles containing norbornene rubber decrease in hardness as the temperature rises, so that the indoor floor surface is not damaged,
There is no discomfort when walking. Therefore, it is possible to provide a comfortable walking state on an ice-snow surface, a normal road surface, and a floor surface.

The anti-slip material of the present invention is lightweight and has excellent properties such as noise-proof, shock-absorbing and heat-insulating properties as well as anti-slip properties. Can be used in various fields where

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between temperature and hardness of particles containing norbornene rubber or a diene rubber foam.

FIG. 2 is a plan view showing one embodiment of the shoe sole of the present invention.

FIG. 3 is a schematic partial sectional view of the shoe sole shown in FIG. 2;

FIG. 4 is a schematic partial sectional view of a shoe sole according to another embodiment.

FIG. 5 is a diagram showing a change in a coefficient of friction of an example and a comparative example.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 9/00 C08L 9/00 45/00 45/00

Claims (7)

[Claims] 1. A non-slip material comprising a diene rubber foam serving as a matrix, in which particles containing norbornene rubber are dispersed and contained. 2. The anti-slip material according to claim 1, wherein the foaming ratio of the diene rubber foam serving as a matrix is 40 to 100%. 3. JIS of particles containing norbornene rubber
The anti-slip material according to claim 1, wherein the hardness at 0 ° C according to K6253-A is 90 degrees or more. 4. The anti-slip material according to claim 1, wherein the glass transition point of the particles containing norbornene rubber is in the range of 15 ° C. to 5 ° C. 5. The anti-slip material according to claim 1, wherein the particle diameter of the particles containing norbornene rubber is 0.1 to 3 mm. 6. A shoe sole comprising the anti-slip material according to claim 1. 7. A first step of blending a norbornene rubber component, a vulcanizing agent and other components as required, vulcanizing and then crushing to produce particles containing the norbornene rubber, Particles, a diene rubber component, a foaming agent,
A method for producing an anti-slip material, comprising a second step of blending a vulcanizing agent and other components as required and vulcanizing.