JP2664229B2 - Anti-slip materials and anti-slip devices for vehicles - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anti-slip material having excellent anti-slip properties on a frozen surface or a snow-covered surface and a non-slip device for a vehicle using the same.

[Prior Art] A spike tire is used as one of slip prevention devices for preventing a vehicle from slipping on a frozen surface or a snow-covered surface. Spike tires exhibit a slip prevention effect by implanting metal studs on the surface of the tire and gripping the road surface with the studs. Because this spike tire has a large anti-slip effect,
Although it is excellent as a non-slip device used on roads on frozen or snowy surfaces, studs protruding from the surface of spiked tires cut off the road surface when traveling on asphalt or concrete pavement surface, and this becomes dust. This causes so-called dust pollution and also causes significant damage to the road surface. Therefore, in recent years, the use of spiked tires has become a serious social issue, and in the near future it is planned to completely abolish this type of spiked tire, and the development of alternative anti-skid devices has been active. It has been done.

One of the major trends is the development of studless tires that use a tread pattern with more incisions and a tread rubber that maintains low hardness even at low temperatures without using studs by improving the road surface graspability of the rubber itself that constitutes the tire. Is progressing. However, the slip resistance of the studless tire is insufficient compared to the spike tire, and the present situation is that the slip of the vehicle body on a frozen surface or a snow-covered surface has not been sufficiently prevented.

Therefore, as another flow, attempts have been made to increase the coefficient of friction with a road surface by mixing various substances into tire rubber.

For example, Japanese Patent Application Laid-Open No. Sho 62-143707 discloses a technique in which a specific short fiber is mixed into a rubber or synthetic resin matrix to form a wheel. In this technology, although the anti-skid property of the tire is slightly improved, the coefficient of friction with the ice surface is small, so that a sufficient slip prevention effect cannot be obtained on the frozen surface, and in addition to running on a general non-freezing road surface. As a result, the short fibers exposed on the tire surface in a very short time are worn or broken, and do not have sufficient durability as a wheel required to have anti-slip properties.

As the same kind of technique, many techniques for mixing ceramic or metal particles into tire rubber have been disclosed. However, even in this technology, there is little adhesion between rubber and particles, so that there is a problem that various kinds of tangential force and circumferential tension acting on the tire during running cause the particles to easily fall off the tire surface. is there.

[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems, makes it difficult for mixed particles to fall off the tire surface, and can maintain an excellent slip prevention effect for a long period of time. An object of the present invention is to provide an anti-slip material which is extremely safe in terms of environmental pollution such as dust pollution and a non-slip device for a vehicle using the anti-slip material.

[Means for Solving the Problems] The problem described above is the anti-slip material in which inorganic particles are mixed in rubber, and the inorganic particles are used in a fourth cycle or a fifth cycle.
IB to IVB coated with at least one metal selected from metals belonging to each group or alloys thereof, wherein the rubber contains an adhesion aid for promoting adhesion between the rubber and the metal. Is achieved by the anti-slip material.

This anti-slip material is particularly suitable as a non-slip device for a vehicle, and is used as a component of a non-slip device for preventing slip of the tire by being mounted on a vehicle tire such as an automobile or a motorcycle, or a ground contact portion of the tire. It can be suitably used.

[Operation] In the anti-slip material of the present invention, the surface of the inorganic particles mixed in the rubber is coated with a specific metal,
Since the metal and the bonding aid are bonded by a chemical bond, the metal-coated inorganic particles (hereinafter, also referred to as “coated inorganic particles”) are firmly bonded to the rubber. And it is extremely difficult to fall off. As a result, when the anti-skid material of the present invention is used as an anti-slip device for a vehicle such as a tire or an anti-slip device mounted on the tire, a good anti-slip effect can be exhibited at a sufficient traveling distance.

[Configuration] Hereinafter, the present invention will be described in detail.

In the present invention, as the inorganic particles to be mixed into the rubber, any substance may be used as long as it is a particle having a sufficiently high hardness that is not easily worn by contact with a road surface.

The inorganic particles are not particularly limited, but are roughly classified into ceramic particles and metal particles.

The ceramic-based material is selected in an extremely wide range, and for example, ceramics such as alumina-based, magnesia-based, zirconia-based, titania-based, and ferrite-based ceramics can be used.

As the metal system, an extremely hard cemented carbide obtained by mixing a metal carbide powder and a metal powder in an appropriate ratio and sintering, for example, WC-Co system, WC-TiC-Co system, WC-TiC-TaC-Co Alloys such as W-Ti, W-Ta, W-Ni and W-Si.

Furthermore, carbon compounds such as WC, TiC, B ₄ C, SiC, TiN, ZrN, SiC
Examples thereof include nitrogen compounds such as N, glass, and particles of natural sand such as silica sand and rocks which cause little harm to the human body.

The inorganic particles preferably have an adhesion area with rubber as large as possible, and are preferably irregular particles having more irregularities on the surface than spherical particles. Further, the inorganic particles may be lightened particles having a hollow portion inside.

The size of the inorganic particles is not particularly limited and can be selected from a wide range, but is preferably 30 μm to 5 mm. When the particle size of the inorganic particles is smaller than the above range, it is difficult to perform a coating treatment with a metal, and when the particle size exceeds the above range, not only is the dispersibility of the rubber deteriorated, but also at the time of contact with a road surface. The impact force received is large, and it is easy to fall off.

The amount of the inorganic particles used is 5 to rubber.
It is preferable to mix 30% by volume. Further, when the inorganic particles are partially used, for example, in the form of islands distributed in a rubber matrix, it is preferable to mix 30 to 90% by volume with respect to the rubber. When the mixing ratio of the inorganic particles is smaller than the above range, the effect of mixing the inorganic particles does not appear remarkably, and the slip prevention effect becomes insufficient. If the use ratio of the inorganic particles exceeds the above range, the rubber may have an adverse effect such as impairing the flexibility.

In the present invention, the metal to be coated on the surface of the inorganic particles includes the metal in the fourth cycle or the fifth cycle.
Metals belonging to each group of IB to IVB or alloys thereof can be used, and Cu-Zn, Cu, Zn, Cu-Sn, Sn, Cu-Zn-Z
n or the like can be preferably used, and in particular, Cu-Zn (brass)
Is preferred. As a method for coating the surface of the inorganic particles with the metal, for example, a plating method such as electroless plating, a vapor deposition method, or the like can be used. Further, the thickness of the metal coating layer is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

In the present invention, as an adhesion aid added to the rubber,
(A) SRH adhesive and (b) cobalt salt adhesive are used.

(A) In the SRH method, the rubber is mixed with silica (hydrous silicic acid), resorcinol as a methylene acceptor, and hexamethylenetetramine as a methylene donor, so that an interface between the rubber and the metal is formed during the vulcanization reaction. It is believed that the formation of the resin promotes the formation of hydrogen bonds, thereby bonding rubber and metal.

M-Aminophenol, melamine and the like can be used in place of the resorcinol, and phenotropin, resotropin, hexamethoxymethylmelamine and the like can also be used in place of hexamethylenetetramine.

The amount of this type of adhesion aid varies depending on the method of addition to the rubber, and cannot be specified unconditionally.

In the (b) cobalt method, a cobalt salt such as cobalt naphthenate or cobalt octenoate is used in order to enhance the adhesion between the rubber and the metal. Although the amount of this type of adhesive aid cannot be specified unconditionally as in the case of the (a) type adhesive aid, it is used in an amount of 1 to 10 parts by weight based on 100 parts by weight of rubber. Although the mechanism of adhesion in the cobalt salt method is not clear, it is considered that cobalt reacts with sulfur as a vulcanizing agent to form a sulfide and at the same time directly contributes to a rubber crosslinking reaction.

As the adhesion assistant, each of the SRH method adhesive and the cobalt salt method adhesive can be used alone, and these can also be used in combination.

The rubber used in the present invention is not particularly limited. For example, natural rubber, styrene-butadiene copolymer rubber, or the like may be used alone or in a blend. In addition, isoprene rubber,
Various rubbers such as isoprene-butadiene copolymer rubber and ethylene-propylene copolymer rubber can be blended and used.

The rubber is usually used as a compounding agent for rubber,
Various additives such as vulcanizing agents such as sulfur and organic peroxides, vulcanizing accelerators such as amines and thiurams, reinforcing agents such as carbon black, and other antioxidants and dispersants can be used. However, the amount of sulfur used as a vulcanizing agent is preferably small because it inhibits the adhesion mechanism between metal and rubber. For example, about 1 to 2 parts by weight is used per 100 parts by weight of rubber.

Next, a process for producing the anti-slip material of the present invention will be described. Although the manufacturing process of the anti-skid material is not particularly limited, for example, the following methods (1) to (3) can be adopted.

(1) At the time of kneading rubber, an adhesive aid and coating inorganic particles are mixed together with a compounding agent such as a vulcanizing agent. At this time,
The coating inorganic particles are preferably kneaded at the final stage of kneading. If the coating inorganic particles are mixed from the initial stage of kneading, a part or most of the coating inorganic particles may be destroyed due to the pressure of the roll and the shearing force during kneading. Is undesirably exposed as a new surface not coated with metal due to the destruction of the metal. Also,
Due to the heat generated during kneading, the metal coated on the surface of the inorganic particles is partially sulfided by sulfur as a crosslinking agent,
There is a possibility that the adhesion to rubber may be reduced.

(2) The surface of the inorganic particles whose surface is coated with the metal is further coated with a rubber mixed with an adhesion aid, and this is mixed into the rubber. At this time, the rubber coated on the surface of the coated inorganic particles is preferably in a semi-vulcanized state, for example, preferably in a stage of a vulcanization degree of 0.3 to 0.6. By doing so, the adhesion between the rubber coated on the surface of the coated inorganic particles and the rubber constituting the matrix is increased, and the adhesion aid can be used efficiently, and the amount used is reduced. Thus, the adverse effect on the rubber as a matrix by the adhesion aid can be reduced.

(3) As still another method, as shown in FIG. 8, a predetermined amount of the coating inorganic particles P is scattered from the hopper 3 on the surface of the rubber sheet S1 drawn from the roller 1, and the upper surface thereof is drawn from the roller 2. Covered with a rubber sheet S2
The coated inorganic particles are sandwiched between the two sheets S1 and S2, and the coated inorganic particles are further pressed by the pressing rollers 4 and 5 to form a single sheet, thereby forming a sheet-like anti-slip material. Note that the pressure rollers 4 and 5 are heated as needed.

[Example] Next, an example of the present invention will be described.

FIG. 1 shows an embodiment in which the anti-skid material of the present invention is applied to a tire. FIG. 1 (A) is a cross-sectional view schematically illustrating the structure of a tire, and FIG. FIG. 2 is a partial cross-sectional view showing a portion B in FIG. 1 in an enlarged manner.

In FIG. 1, a tire 10 is provided with a carcass 16 and a bead 14 which form a skeleton of the tire outside a rim 12, and a cord layer for reinforcing the carcass 16 is provided on the outer periphery of the carcass 16.
19 is provided, and a rubber layer 18 is provided on the outer periphery thereof.
And, to support the vehicle weight on the ground portion of the rubber layer 18, and to withstand the impact and friction with the road surface due to fast rotation,
A thick tread portion 18a is formed. Various tread patterns are formed on the tread portion 18a so that the tread portion 18a firmly grips the road surface when moving forward, maneuvering, and stopping.

The tread portion 18a is composed of two layers of different rubber components, the inner first tread layer T1 is composed of a normal tire rubber component constituting the entire rubber layer 18, and the outer second tread layer The layer T2 is made of the anti-slip material of the present invention.

The second tread layer T2 is preferably provided on the entire contact portion of the tire 10, and in this manner,
The slip prevention effect can be maximized. As shown in FIG. 1 (B), the thickness of the second tread layer T2 is d from the surface of the tread portion 18a to the bottom of the groove S, and the thickness of the second tread layer T2 is d1. Then d1
= 0.5d-0.8d is preferred.

 Next, the operation of the present embodiment will be described.

In the present embodiment, by providing the second tread layer T2 made of the anti-slip material of the present invention on the surface of the tread portion 18a, the effect of preventing the tire 10 from slipping can be remarkably increased.

That is, the second tread layer T2 is made of rubber in which the coating inorganic particles are dispersed, and the inorganic particles P partially exposed on the surface are innumerable. And into the snow compacted surface, significantly increasing the road surface grasping force of the tread 18a,
It is possible to effectively prevent slip on the frozen surface or the snow-covered surface.

What is particularly characteristic of the present invention is that the inorganic particles P are firmly adhered to the rubber by mutual chemical bonding between the metal coated on the surface thereof and the bonding aid compounded in the rubber. As a result, the rubber layer is unlikely to be separated from the rubber layer even by severe external force received during traveling, and its slip prevention effect can be maintained over a long traveling distance.

Furthermore, when the anti-skid material of the present invention is used, damage to the road surface is extremely small as compared with a spike tire or the like in which metal studs are embedded because the particle diameter of the inorganic particles exposed in the ground contact portion is small. It is also less likely to cause environmental pollution, such as dust pollution, due to its small size and small cutting power.

FIG. 2 is an explanatory partial sectional view showing another embodiment in which the anti-skid material of the present invention is applied to a tire. The tire 10 shown in this example has the same basic structure as the tire shown in FIG. 1, and the same members are denoted by the same reference numerals and the detailed description thereof will be omitted.

This embodiment is different from the above embodiment in that a third tread layer T3 made of another rubber layer is formed on the surface of the tread portion 18a. This third tread layer T3
Is composed of a rubber that has abrasion resistance that is easy to wear about 1/2 or less as compared to normal tire rubber, and has a thickness of 0.5 to 2
mm. Such abrasion-resistant rubber is
It is obtained by reducing the carbon black as a reinforcing agent to 1/2 or less of ordinary tire rubber, or by reducing the molecular weight to 1/2 or less compared to ordinary tire rubber,
As such a rubber, for example, a styrene-butadiene copolymer or the like can be used.

Such a third tread layer T3 wears at a traveling distance of 50 to 100 km because of its low wear resistance, and the second tread layer made of the anti-slip material of the present invention at the ground contact portion.
T2 will be exposed. As a result, only the surface of the groove portion S formed in the tread portion 18a is in a state of being coated with the third tread layer T3. Therefore, even if the inorganic particles P are present on the surface of the second tread layer T2, since the surface is coated with the third tread layer T3, the inorganic particles P exposed from the second tread layer T2 are formed. Can serve as a nucleus to prevent cracks from occurring at the groove bottom.

FIG. 3 and FIG. 4 are explanatory side views showing still another configuration example when the anti-skid material of the present invention is applied to a tire.

In these examples, the anti-slip material of the present invention is partially used for the tread portion 18a of the tire, and as shown in FIG. 3, the tread portion T4 made of the anti-slip material of the present invention is formed along the circumference of the tire. A tread portion T5 made of the anti-slip material of the present invention as shown in FIG.
May be arranged in an island shape.

As described above, the anti-slip material of the present invention is applied to the tread portion 18 of the tire.
When partially used in a, it is preferable to use a rubber component for a studless tire in a portion of the tread portion T6 or T7 other than the tread portion T4 or T5 made of the anti-skid material of the present invention. By using the anti-slip material of the present invention and the rubber component for a studless tire together in the tread portion 18a, it is possible to synergistically exhibit the slip prevention effect of both, and the road surface caused by the mixed inorganic particles is Pollution-free studless tires with minimal damage can be supplied. In this case, it is preferable that the tread portion constituted by the anti-slip material of the present invention is formed in a block shape in which the coating inorganic particles as small as possible are filled at a high density.

As described above, the anti-skid material of the present invention can be used on the entire surface or a part of the tread portion of the tire, and can also be used on the entire rubber layer of the tire.

When forming a tire using the anti-slip material of the present invention,
It is basically the same as a normal tire, and can be used in combination with a normal tire rubber or alone when molding the tire. In addition, the anti-slip material of the present invention can also be used in the manufacture of so-called corrected tires, in which the tread portion of the tire is re-used for the purpose of recycling the tire. A retreaded tire can also be constituted by using a partially or partially used tire.

Fig. 5 shows an example in which the anti-slip material of the present invention is applied to a belt-shaped anti-slip device for a tire. Fig. 5 (A) is a plan view thereof, and Fig. 5 (B) is a side view thereof. Show.

The belt-shaped anti-slip device 20 of this embodiment has a belt portion 22 to which the anti-slip material of the present invention is applied, and the belt portion 22 has a large number of anti-slip projections 24 formed on the ground contact side.

The belt portion 22 has at least its anti-slip projection 24 made of the anti-slip material of the present invention.
When 20 is wound around the outer periphery of the tire 10 as shown in FIG. 6 and affixed with an adhesive, the same anti-slip effect as described in the embodiment of the tire can be exerted. It should be noted that this type of anti-slip device 20 can be peeled off when it is no longer needed, so that the tire 10 can be used continuously.

EXPERIMENTAL EXAMPLES EXPERIMENTAL EXAMPLE 1 First, Cu-Zn (60:40) was coated on a surface of silica sand having a particle size of 250 to 500 mesh by electroless plating to a film thickness of 2 to 3 μm. The coating inorganic particles were mixed with the rubber composition at the final stage of rubber kneading so that the volume ratio of the inorganic particles to the rubber was 10%. In addition, the compounding ratio of the rubber used here is as follows.

(Blending ratio) Natural rubber 100 parts by weight Carbon black ISAF 60 parts by weight Process oil 30 parts by weight Sulfur 2 parts by weight Cobalt naphthenate 1.5 parts by weight Using a mixture of the above rubber composition and coating inorganic particles, shown in FIG. A sample of the belt-shaped anti-slip device 20 was formed. The sample of this belt-shaped non-slip device has a width of about 65 mm and a thickness of about 8.5 mm. This belt-shaped anti-slip device is referred to as “anti-slip device A”.

Experimental Example 2 The mixing ratio of coating particles was 20% by volume based on rubber.
A belt-shaped anti-slip device was formed in the same manner as in Experimental Example 1 except for the above. This belt-shaped anti-slip device is referred to as “anti-slip device B”.

Comparative Experimental Example 1 A belt-shaped anti-slip device was formed in the same manner as in Experimental Example 1, except that silica sand particles were used without being coated with a metal. This anti-slip tool is referred to as "anti-slip tool C".

(Experimental method) Non-slip devices A to C were attached to the outer periphery of the front wheel of a front wheel drive vehicle, and two occupants traveled on a concrete road surface or an asphalt road surface in a general urban area, and visually observed the falling state of the coating particles. The ratio of the remaining coating particles per unit area was examined.

(Experimental results) The sliding devices A and B according to the present invention travel 1000 km.
With 70 of the coating particles exposed on the surface of the non-slip device
It was confirmed that 8080% remained.

On the other hand, the non-slip device C outside the scope of the present invention is:
Approximately half of the silica sand particles exposed on the surface of the anti-slip device were dropped off when traveling 100 km, and it was confirmed that most of the silica sand particles were dropped off at a travel distance of 1000 km.

FIG. 7 is an explanatory view showing another embodiment of a ladder-type belt-shaped anti-slip device. In this example, a plurality of side wires 32 having a fastening portion at both ends are provided between a plurality of side wires 32. The belt portion 34 is arranged and fixed at a predetermined interval. The belt portion 34 is made of the anti-slip material of the present invention, similarly to the belt portion 22 described in the above embodiment. If the belt-shaped anti-slip device 30 is mounted on a tire, an excellent anti-slip effect can be exhibited at the ground contact portion.

As described above, when the anti-skid material of the present invention is used around a tire to be used as a so-called non-metal chain, the form is not limited to the above-described embodiment, and takes a very wide variety of forms such as a net type and a sheet type. be able to. Also, in such a non-metal chain, as in the case of the tire, the rubber component for a studless tire and the anti-slip material of the present invention can be used together to form a ground contact portion. The block portion in which the coating inorganic particles are mixed at a high density may be configured to be distributed in a matrix of a rubber component of a studless tire in various patterns such as an island shape.

The anti-slip material of the present invention and the anti-slip device for a vehicle to which the anti-slip material is applied have been described above. However, the anti-slip material of the present invention is extremely suitable as an anti-slip device for a vehicle. The invention is not limited as long as it is used for the purpose, and may be applied to the tire itself, or may be used as a chain-type anti-slip device mounted on the tire and capable of preventing its slip.

[Effects of the Invention] According to the present invention, by mixing specific coating inorganic particles into rubber, the structure is simple, the anti-slip effect is excellent, and when used as a non-slip device for vehicles, dust pollution and the like are prevented. It is possible to provide an anti-slip material and an anti-slip device for a vehicle, which are less likely to cause slippage.

[Brief description of the drawings]

FIG. 1 shows an example in which the anti-skid material of the present invention is applied to a tire. FIG. 1 (A) is a cross-sectional view schematically illustrating the structure of a tire, and FIG. 1 (B) is an enlarged view of a portion B in FIG. 2 to 4 are explanatory views showing another embodiment in which the anti-skid material of the present invention is applied to a tire. FIG. 5 is a belt-like slip-proof material of the present invention. An example in which the present invention is applied to a stopper is shown, (A) is a front view thereof, (B) is a side view thereof, and FIG. 6 is a state in which the belt-shaped anti-slip device shown in FIG. FIG. 7 is an explanatory view showing another embodiment in which the anti-slip material of the present invention is applied to a belt-shaped anti-slip device. FIG. 8 is an example of a method of manufacturing the anti-slip material of the present invention. FIG. 10 Tire 18 Rubber layer 18a Tread layer 20 Belt-shaped non-slip device 22 Belt portion 30 Belt-shaped non-slip device 34 Belt portion

Claims (4)

(57) [Claims] An anti-slip material in which inorganic particles are mixed in rubber, wherein the inorganic particles are used in a fourth cycle or a fifth cycle.
B is coated with at least one metal selected from metals belonging to each group of IVB or an alloy thereof, wherein the rubber contains an adhesion aid for promoting adhesion between the rubber and the metal. And anti-slip material. 2. The method according to claim 1, wherein after the surface of the inorganic particles is coated with a metal, the surface is further coated with a rubber mixed with an adhesion aid and mixed with the rubber. 2. An anti-slip material according to claim 1. 3. A vehicle tire characterized in that at least a tread portion of the tire is entirely or partially constituted by the anti-slip material according to claim 1. 4. A non-slip device for a vehicle, wherein at least a ground contact portion is entirely or partially formed of the anti-slip material according to claim 1.