KR101549687B1 - Method for manufacturing four season type tire or outsole and the product thereby - Google Patents

Abstract

The present invention relates to a method for producing an anti-slip material for seasonal seasons and a non-slippery material produced by the method. The slip-resistant material comprises a top rubber as a temperature-responsive rubber composition in contact with a ground surface for spikes, At least one laminated rubber, which is a rubber composition for bonding interposed between the upper rubber layer and the dissimilar rubber layer, is laminated in a molding die; A non-slip anti-slip chain tire or a four-seasons type outsole made by the method according to the present invention is characterized in that it comprises an upper rubber layer and a lower layer rubber layer, The dissimilar rubber has a sufficient adhesion force by the laminated rubber.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a four-seasons slip resistant body by simultaneous vulcanization and simultaneous molding, and a slip prevention body produced by the method.

In the above and below, the slip prevention body means a tire or a shoe outsole.

The present invention relates to a method of manufacturing an anti-slip device for seasonal seasons and a non-slip device manufactured by the method. More particularly, the present invention relates to an anti- Slippery body such as an outsole is prevented from slipping easily on a snowy surface, and a non-slippery body manufactured by the method.

Background Art [0002] In general, a snow chain attached to a tire of an automobile, or an eigens used in combination with shoes, a non-slip product to be attached to a shoe outsole or equipped with a spike on an outsole to prepare for sliding is widely known.

However, these non-slip mechanisms are inconvenient to attach and detach to shoes or tires, have a low friction with an object, and are weakly attached to shoes or tires.

In addition, it is cumbersome to manufacture, inconvenient to attach and detach, and expensive to manufacture.

With respect to this anti-slip mechanism, many prior arts, including Japanese Patent No. 3757238 and Korean Patent No. 1327212, disclose a method of attaching a rubber spike to a tire groove already formed, This is an example in which simultaneous vulcanization or simultaneous molding is difficult and a post-mounting method in which the bonding is weak is adopted.

Among these non-slip mechanisms, in particular, a metal spike or a tire having a spike made of a non-metallic material is required to be attached to spikes and is subject to a regulation that the tire must be replaced with a normal tire other than the winter season due to dust pollution, The road surface can not be urgently dealt with immediately, and there are various problems such as storage cost.

Further, in the case of rubber spikes, the post-mounting method is applied because the polymer blend (hereinafter referred to as PB) composition for the spike is bonded to the rubber material constituting the tire body or the shoe outsole body This is because the adhesive strength is very weak.

In addition, the PB rubber composition disclosed in the prior art corresponds to peroxide crosslinking, and is not capable of simultaneous vulcanization with a different kind of rubber for tire or outsole. Moreover, the method of attaching the adhesive also has a weak adhesive strength due to poor adhesive property.

1. Japanese Patent No. 3757238 (Jan. 13, 2006) 2. Registration No. 0581776 (May 05, 2006) 3. Registration No. 0631151 (Mar. 28, 2006) 4. Registration No. 1139945 (April 18, 2012) 5. Registration No. 1148212 (2012.05.15) 6. Registration No. 1327212 (November 3, 2013)

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described problems of the prior art and has been made to solve the above problems, and it is an object of the present invention to eliminate the concept of a spike of a rear mounting type, and to use it as a pair of four seasons- A method of manufacturing a non-slip body corresponding to a four seasons that can maintain a good bonding property by having sufficient adhesion between a PB composition for an upper layer rubber (for spike) and a different rubber (tread of a tire or a rubber for a shoe outsole) And a main object thereof is to provide a slip prevention body manufactured by the method.

In addition, the present invention provides simultaneous vulcanization molding while exhibiting a spike effect by providing a concavo-convex pattern of a spike-shaped body in a tire molding metal mold, not requiring post-mounting and adhesion, So that it becomes unnecessary to replace the tire, and it is another object of the present invention to always ensure safety in response to an urgent road surface change.

In addition, the present invention provides simultaneous vulcanization molding while exhibiting a spike effect by providing a concavo-convex pattern of a spike-shaped body in a molding die for a shoe outsole, and does not require post-mounting and adhesion, There is another purpose in making shoes available as outsole.

The present invention provides, as means for attaining the above-mentioned object, a rubber composition comprising a top rubber as a temperature-responsive rubber composition for contacting a ground surface for spike, a dicom rubber as a rubber composition constituting a tire body or a shoe outsole body, At least one laminated rubber, which is a rubber composition for bonding interposed between the rubber and the dissimilar rubber, is laminated in a mold for molding; And the rubber laminated in the molding die is simultaneously vulcanized and molded to form a non-slip body.

At this time, the upper layer rubber is preferably formed of a polymer blend (PB) in which acrylonitrile-butadiene rubber (NBR) is limited to 185 ± 10 parts by weight based on 100 parts by weight of polyvinyl chloride (PVC) .

The NBR may be a hydrogenated NBR, a carboxylated NBR having an acrylonitrile content of 31 to 44 wt%, or a combination thereof.

In addition, the dissimilar rubber is composed of NR (natural rubber), IR (isoprene rubber), SBR (styrene-butadiene rubber), BR (butadiene rubber) alone or a combination thereof, Or may be a terpolymer.

In addition, as the laminated rubber, a polymer selected from a homopolymer of isoprene, a homopolymer of butadiene and a copolymer of butadiene is selected, and the sum of the content of isoprene and butadiene in the selected polymer is Is 50% by weight or more of the polymer selected.

Furthermore, the vulcanizing conditions of the upper rubber layer and the laminated rubber are preferably the same as those of the vulcanized rubber.

In addition, the present invention also provides a non-slip body manufactured by the above-described manufacturing method.

According to the present invention, the upper layer rubber and the dissimilar rubber have a sufficient adhesive force by the laminated rubber when the slip-resistant body which can be used as a four seasons-compatible tire or a four seasons-compatible outsole is manufactured.

Further, by providing a concave-convex pattern of a spike-shaped body in a molding die for molding a tire or a shoe outsole, simultaneous vulcanization molding is performed while manifesting a spike effect, and there is no need for post-mounting and adhesion, (Or a shoe outsole) becomes unnecessary, safety can be assured at all times by immediately responding to an urgent road surface change.

1 is a conceptual sectional view showing a laminated structure according to the present invention,
Fig. 2 is an exemplary view of a cross section formed by vulcanization,
3 is an example of a spike shape,
4 is a view showing an upper rubber layer disposed on a tire tread portion,
FIG. 5A is a plan view and a sectional view of the sheet of FIG. 1 cut in a slit shape,
FIG. 5B is a view showing a laminated structure of a tire and an unvulcanized green sheet,
FIG. 5C shows an upper layer rubber and a laminated rubber wound on a tire in a ring form,
Figure 6 shows a cross-section of various types of spikes arranged in the belt-shaped sheet of Figure 5a,
7 is a view for explaining a wet effect in the present invention,
8 is a view for showing that the present invention is applied to a rubber infill,
Figs. 9 to 11 show various laminated structures in which an upper layer rubber and a laminated rubber are laminated on a tire raw paper. Fig.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

Before describing the present invention, the following specific structural or functional descriptions are merely illustrative for the purpose of describing an embodiment according to the concept of the present invention, and embodiments according to the concept of the present invention may be embodied in various forms, And should not be construed as limited to the embodiments described herein.

In addition, since the embodiments according to the concept of the present invention can make various changes and have various forms, specific embodiments are illustrated in the drawings and described in detail herein. However, it should be understood that the embodiments according to the concept of the present invention are not intended to limit the present invention to specific modes of operation, but include all modifications, equivalents and alternatives falling within the spirit and scope of the present invention.

An object of the present invention is to provide a thermosensitive rubber composition for spiking which comprises an upper rubber layer which is a temperature responsive rubber composition which comes into contact with a ground surface and a rubber composition which is a rubber composition constituting a tire body or a shoe outsole body and an adhesive interposed between the upper rubber layer and the dissimilar rubber (Or an outsole), and a sufficient peeling strength is ensured by simultaneously completing the vulcanization and the molding of the tire, thereby producing a four-seg- Thereby providing a non-slidable body.

At this time, the upper layer rubber is a polymer blend, that is, PB (hereinafter referred to as " PBB ") in a ratio of 175-195 parts by weight of NBR (acrylonitrile-butadiene rubber) to 100 parts by weight of polyvinyl chloride And 0.5 parts by weight of St / Ca: stearic acid / calcium, St / Zn: stearic acid / zinc, St / Ba: barium stearate and wax were added, Composition (i.e., basic PB).

Here, the NBR is particularly preferably a hydrogenated NBR (hereinafter referred to as 'HNBR'), and a combination of HNBR and carboxylated NBR (hereinafter referred to as 'XNBR') may be used, which is suitable as an upper rubber for a tire .

In this case, the reason for limiting the NBR to the above range is to maintain the volumetric capacity of PVC to enable the sulfur flow. When the NBR is added in an amount less than 175 parts by weight, the volume of the PVC in which the sulfur flow is not established is increased , The addition of more than 185 parts by weight reduces the volume of PVC and the control of the glass transition temperature is broken and the function of stiffening the spike becomes defective.

In addition, the NBR is preferably an XNBR containing 31 to 44% by weight of acrylonitrile, and may be a combination of HNBR and XNBR, which is suitable as an upper layer rubber for shoe outsole.

At this time, acrylonitrile should be contained in the above range within the above-mentioned components of the NBR. When acrylonitrile is added in an amount of less than 31% by weight, the amount of double bonds due to the reaction becomes small, The compatibility of the PVC with the polar resin is good, but when it exceeds 44 wt%, the effective area of the vulcanization is lowered and the peel strength of the adhesive is lowered.

In addition, the blending method of the PB is performed by preheating in the range of 125 to 155 ° C. in an internal mixer, mixing the mixture at a temperature of 130 to 140 ° C. for 5 minutes in a stock, and performing heat plasticization After confirming the occurrence, the auxiliary materials excluding sulfur are continuously mixed, and the mixture is mixed at 130-140 ° C. for 5 minutes. Then, the mixture is kneaded and sheeting is performed while the mixed compound is stored in a sheet form.

In this process, the sulfur is added and mixed in the required amount on the chill roller at the time of use.

St / Ca: stearic acid / calcium, St / Zn: stearic acid / zinc, St / Ba: barium stearate, and wax are additives for improving the functionality.

On the other hand, the dissimilar rubber may be a tread / cushion / carcass rubber constituting the tire body, and may be made of natural rubber, IR (isoprene rubber), styrene-butadiene rubber (SBR) Or a mixture thereof, and is a diene polymer mainly made of a monomer having a conjugated double bond, or a terpolymer such as NBIR containing isoprene.

The same applies to the rubber for shoe outsole.

The laminated rubber to be brought into contact with the dissimilar rubber is selected from a polymer selected from the group consisting of a homopolymer of isoprene (IR, NR), a butadiene homopolymer (BR), a butadiene copolymer (SBR, NBR) The total content of isoprene and butadiene should be maintained at 50 wt% or more of the total polymer.

Particularly, the present invention is characterized mainly by a simultaneous molding and a simultaneous vulcanization technique. This is because a laminated form in which at least one sheet (laminated rubber) is superposed between an upper rubber layer and a different rubber layer is used, And is vulcanized and molded under the same conditions as the vulcanization time.

That is, the vulcanization curve of the upper layer rubber and the laminated rubber of the present invention is vulcanized to have the same vulcanization condition as that of the different rubber.

Of course, in the case of a footwear outsole, the upper layer rubber and the laminated rubber are vulcanized under the same conditions as the vulcanization temperature and vulcanization time of the outsole for the different rubber.

In particular, the upper layer rubber is a rubber composition for controlling the glass transition temperature, and the polymer preparation of the present invention uses a master batch of an on-site preparation method using an internal mixer and a mixing mill.

Of course, a wet master batch system in which a polymer specified in the present invention is mixed with an emulsion and a latex form, a wet master batch, a reinforcing agent, and an inert filler are mixed, .

In other words, the composition according to the present invention is based on sulfur volatilization, and when the content of XNBR or HNBR in the acrylonitrile is increased, compatibility with the polar resin of the PVC is improved but it should not be added excessively. do.

In particular, the amount of double bonds in the main chain is reduced by the hydrogenation reaction of HNBR, and when the hydrogenation rate is increased, the sulfur flow becomes difficult.

Therefore, HNBR having a hydration rate of 95% or less should be used, and a hydration rate of 95% is the limit of sulfur.

In addition, since the iodine value of HNBR affects the glass transition temperature (Tg ° C), the upper rubber should be a straight resin having an average degree of polymerization of PVC of 1000 ± 300, and the melting of the dry blend of NBR An area of temperature and kneading temperature should be set.

For instance, the solubility of PVC integer (hereinafter referred to as 'SP value') is ^{9.55 (cal / cm 3) 1/2} , SP value of the XNBR or the HNBR of the invention is ^{9.8 ~ 10.4 (cal / cm 3} ) 1 / ² , the composition ratios specified in the present invention can easily melt each other.

However, NR, SP value ^{7.9 ~ 8.35 (cal / cm 3} ) ^1/2 of the tread of the IR, SP value of ^{BR 8.4 (cal / cm 3)} 1/2, SP value of the ^{SBR 8.55 (cal / cm 3)} 1 ^{/ 2} , the SP value of PVC is 9.55 (cal / cm < ³ &^gt;) ^1/2, which is located at a high value.

In addition, there is no sulfur flow between the molecules of PVC, and it has a property of softening as a resin at high temperature, and the volume of PVC which is not able to flow sulfur by 65% of NBR is 35% (NBR 185 parts by weight is added).

Therefore, if such a PVC volume is reduced, the control of the glass transition temperature is broken, and the function of stiffening the spike is poor.

Therefore, the vulcanization of the contact area between the upper rubber of the present invention and the laminated rubber brought into contact with the upper rubber is such that 65% of the upper rubber is vulcanized and the vulcanized effective area is reduced by 35% It can be a cause of deterioration.

In order to solve this problem, in the present invention, a process of preliminarily mixing powdered rubber vulcanized with NBR in PVC is preliminarily carried out. The vulcanized powder rubber does not dissolve with each other and is only dispersed and reduces the area of PVC in proportion to the amount of addition, The exposed grains of the exposed particles are widened to reduce the hard-adhering area of the PVC.

For example, the addition of 100 parts by weight of powdery rubber vulcanized to 100 parts by weight of PVC sets the adverse effect area to 0 (zero).

In addition, even in thermoplastic PVC, the powder rubber does not melt and becomes attached granule form, becoming the form of islands of PVC sea and cross-linked powder.

As a result, the PVC area is reduced by half, the protruding particles are doubled, and a strong bonding surface with the laminated rubber can be secured.

The modified PVC of the present invention modified by vulcanized powder rubber completely eliminates the influence of PVC (not crosslinkable) despite the blending ratio of PVC and NBR of the present invention.

In particular, if it is made in the form of a very thin sheet, it can become a lower layer rubber (a lower layer rubber located immediately below the upper layer rubber) which enables sulfur vulcanization and solves the adhesion problem incorporated on the bottom side of the upper layer rubber.

In addition, as for the modification effect of the NBR powder, the adhesion effect is improved in proportion to the amount of the blend, the hardness is secured without softening at a high temperature in proportion to the amount of the blend, the high temperature response function is maintained, Resilience, permanent deformation, and high strength are modified.

Examples of commercially available powdered rubbers (JP / ZEON CORPORATION) include powdered NBR such as NipolHF21, Nipol1411, and Nipol422. Examples of the rubber other than powders include partially crosslinked NBR such as NipolDN214, NipolDN631, and Nipol1072u, and Nipol1009 , Hot SBR (hot SBR) crosslinked with divinylbenzene (C ₁₀ H ₁₀ ) and the like, such as Nipol SBR1009, etc., can be expected to have the same effect as powder NBR.

In addition to the above-mentioned commercially available rubber, the effects of polychloroprene (hereinafter referred to as "CR"), HCR (Heat Cured Rubber), ACM (acrylic rubber) have.

Accordingly, in the present invention, it is possible to provide a surface modification effect by providing a cohesive layer adhered directly below the upper layer rubber by using the above-mentioned powder rubber commercial product, By weight based on 100 parts by weight of the resin.

For example, one or more of NipolHF21, Nipol1411 and Nipol422 may be mixed in an amount of 35 parts by weight or less based on 100 parts by weight of the base rubber composition, or 35 parts by weight or less of one or more of NipolDN214, NipolDN631 and Nipol1072u Or NipolSBR1009 is mixed in an amount of 35 parts by weight or less, or the like.

Moreover, examples of the formulation that can be performed by considering a number of functionality, with respect to the upper rubber base composition 100 parts by weight, VN3 (Hydrous-silica) 15 parts by weight, TiO ₂ 15 parts by weight, ZnO (Vulcanization accelerator) 3.5 parts by weight 1 part by weight of C (N-cyclohexybenzothiazole-2-sulfenamide), 0.32 parts by weight of D (1,3-DIPHENYL GUANIDINE) and 1.4 parts by weight of S (Sulfur) are most preferably used.

On the other hand, the laminated rubber is a polymer selected from a homopolymer of isoprene, a homopolymer of butadiene and a butadiene copolymer, or a combination of two or more kinds selected from the group consisting of isoprene and butadiene. The total content of isoprene and butadiene in the polymer is 50% Or more.

In this case, the laminated rubber may have a multi-layered form of an upper layer and a plurality of intermediate layers, and may have at least one auxiliary layer in some cases.

For example, the upper layer, the intermediate layer, and the at least one auxiliary layer may be formed of at least one of ZnO, St / Ca, VN-3, PEG (polyethylene glycol), DOP (Dioctyl phthalate), NZ-cyclohexybenzothiazole- , 3-DIPHENYL GUANIDINE), S (Sulfur), HAF (carbon black), BR1220 (Nipol BR1220: ZEON CORPORATION), N280 (JSR N280: JSR CORPORATION) and SBR1502 (Nipol SBR1502: ZEON CORPORATION) And specific examples thereof will be described later with reference to examples.

For example, in the tire of the present invention, since the upper layer rubber is a temperature-responsive composition having super abrasion resistance, it runs on a dry road surface as a normal tire, exhibits a spike function on an ice road surface, It exhibits a caterpillar function and has a structure composition that exhibits wetting resistance (WET resistance) in rain.

In the tire molding die, a plurality of U-shaped ditches in the form of a groove are provided on the center side of the tread from both sides (shoulder portions), and ring-shaped irregularities are formed thereon.

In this case, the shape of the concavo-convex shape of the mold is 10 ± 5 mm in width and 8 ± 1 mm in depth, and the thickness of the upper rubber layer is preferably 1 to 3 mm, and it is designed according to the vehicle weight and tire size.

In addition, the thickness of the laminated rubber can be changed according to the thickness of the tread and the depth of the ditch (about 8 mm) of the mold.

In addition, the upper layer rubber and the laminated rubber can be stuck to the tire circumference (the circumference of the dissimilar rubber) in the form of a string to determine the position corresponding to the U-groove. Alternatively, it is also useful to pre-load the upper layer rubber and the laminated rubber in the U-shaped ditch of the mold.

Further, the area of the dry road surface is approximate to the area and shape of a normal tire, and a new trench is prepared near the U-shaped groove (groove) and the side wale, and the uneven pattern is arranged in the trench in an arbitrary shape .

The concavo-convex pattern is provided with a triangular-shaped tip portion (edge) formed at a sharp angle and a tip portion in the form of a pedestal for coping with rainfall, and the shape and the quantity of the pattern are preferably provided in accordance with the tire size.

Furthermore, a rubber composition (hereinafter, referred to as "WET blend") for 'increasing friction resistance at the time of wetting' may be separately laminated on the lower layer of the tip portion in the form of a pedestal corresponding to the rainfall. The tip is in the form of a pedestal, the upper rubber is very thin, and the WET formulation is exposed after the film is worn during driving, resulting in a WET effect.

The production of the four-seasons slip resistant body manufactured by the simultaneous vulcanization and simultaneous molding method according to the present invention may have the form as shown in FIGS. 1 to 11.

For example, FIG. 1 shows a laminate cross-section with an upper rubber layer.

In FIG. 1, reference numeral 1 denotes an upper rubber layer, reference numeral 1 denotes a lower rubber layer which is incorporated into a very thin sheet on the bottom side of the upper rubber layer, reference numeral 2 denotes a laminated rubber including crushed particles, , (3) shows the tire side, and (4) shows the enlarged particles of the crushed particles.

Fig. 2 shows a vulcanization-molded section. For example, Fig. 10 shows a spike-shaped body, for example, a triangular spike, Fig. 20 shows a pedestal, (24), (26) and (28) show a reticulated pattern as a laminated rubber.

In FIG. 3, reference numeral 10 denotes a triangular spike, reference numeral 20 denotes a spike-shaped spike, and reference numeral 30 denotes a U-shaped spike.

4A and 4B show a top view and a cross-sectional view of a slit-shaped body in the form of a strip in the sheet of FIG. 1, and FIG. 5B is a cross- FIG. 5B shows an upper layer rubber and a laminated rubber wound around the tire in the form of a ring, and FIG. 5B shows the upper layer rubber and the laminated rubber wound around the tire in the form of a ring.

6 also shows a cross section of the triangular spike 10, the pedestal 20 and the U-shaped spike 30 of FIG. 3 arranged in the belt sheet of FIG.

7 shows a state before the abrasion, and a center view shows a state in which the left side is worn and the right side shows the function of the dispersed ebonite particles 50. In Fig.

That is, when the crushed particles are worn out sequentially from the upper layer rubber 1 to the lower layer and the crushed particles are larger than the water film between the road surface 40 and the tire ground plane, the wet effect as shown in the figure is exhibited, and the upper and lower arrows indicate the thickness of the water film.

At this time, the dispersed ebonite particles 50 in the upper layer rubber 1 have no relation to the temperature response, and are stiffened under the freezing point from the beginning. The remaining upper layer rubber 1 after the surface is worn acts in the same form, 1) as an edge at the ice sheet surface.

In other words, the packed road surface 40 and the ebonite particles 50 become fine particles to improve friction on the dry road surface, and on the rainy road surface, fine particles are interposed between the water films to eliminate the lubricity of the water film.

Therefore, it has an effect on hydroplaning of high-speed driving.

8 (a) shows a cross section of a rubber coated fabric which is commonly practiced in a conventional rubber belt manufacturing method, (b) shows engraftment, and , And the laminated rubber of the present invention is thinly topped and adhered to both surfaces of the cloth by dissolving the laminated rubber on the dotted line, and (b) shows the plane of the cloth. That is, the present invention may also be embodied in the form of rubber infill.

9 shows that the upper layer rubber raw paper 60 and the laminated rubber raw paper 60 'are sheared by 1 to 1.2 mm in calender to 5.5 mm of the intermediate layer 70 and the sheets are bonded to the intermediate layer 70 in the form of a sandwich And a sectional view showing a squeezed section, and reference numeral 80 denotes tire raw paper.

10 is a cross-sectional view of the upper layer rubber raw paper 60 and the laminated rubber raw paper 60 ', sheeting the intermediate rubber layer 60 and the laminated rubber raw paper 60', and pressing them together.

11 shows a cross section of an upper layer rubber raw paper 90 and a layer (1 to 3 mm) laminated rubber raw paper 60 directly attached to the tire raw paper 80. Fig.

[Example]

Hereinafter, embodiments according to the present invention will be described.

First, a basic component constituting the upper layer rubber of the present invention, that is, a basic PB (polymer blend) will be described.

The upper rubber is PB which becomes rigid at the freezing point below 0 ℃ and becomes flexible at room temperature. That is, since the upper layer rubber should be a rubber composition having temperature responsiveness, it is formed as shown in Table 1.

Basic PB of upper rubber 100 parts by weight of PVC NBR (XNBR or HNBR) 185 占 10 parts by weight 0.5 parts by weight of St / Ca, St / Zn, St / Ba and Wax In the temperature range of 130 ° C to 155 ° C,

St / Ca: stearic acid / calcium, St / Zn: stearic acid / zinc, St / Ba: barium stearate

Table 2 shows an example of a lower layer rubber, that is, a laminate layer adhering to the lower side of the upper layer rubber, and the laminate layer is classified into an upper layer rubber.

With respect to 100 parts by weight of the upper rubber base PB of Table 1 No.1: NipolHF21 / Nipol1411 / Nipol1422 35 parts by weight No.2: NipolDN214 / NipolDN631 / Nipol1072u 35 parts by weight No.3: NipolSBR1009 35 parts by weight No.1 to No.1 were added to 100 parts by weight of PB. Add one of three

Table 3 shows the preferred implementation of the upper layer rubber.

With respect to 100 parts by weight of the basic PB of the upper rubber of Table 1 VN3 (Hydrous-silica) 15 parts by weight TiO ₂ 15 parts by weight ZnO (Vulcanization accelerator) 3.5 parts by weight CZ 1 part by weight D 0.32 parts by weight Sulfur 1.4 parts by weight Thickness of 1.3mm, seat in calender

(CZ: N-cyclohexybenzothiazole-2-sulfenamide, D: 1,3-DIPHENYL GUANIDINE)

Table 4 shows a preferred embodiment of a coalescing layer adhered directly below the upper layer rubber.

Implementation of coalescence layer Mixing ratio The formulation of Table 3 About 100 parts by weight No.1 in Table 2 35 parts by weight

Thus, the non-slip piece according to the present invention was sheared at a calender with a thickness of 0.3 mm, and an upper layer sheet (2 mm) + a lower layer sheet (coalesced layer) (0.3 mm) 6 sheets (laminated rubber), and pressing them on rollers.

Table 5 shows a preferable implementation of the laminated rubber. Layers constituting the multilayered structure are the same as Nos. 4, 5 and 6, and No. 7 is an example of the auxiliary layer.

No.4 Upper layer combination No.5 middle layer No. 6 middle layer No. 7 auxiliary layer NBR: 85 / PVC: 15 weight ratio of 100 parts by weight of the mixture With respect to 100 parts by weight of NBR containing 24% by weight of acrylonitrile With respect to 100 parts by weight of NBR containing 20% by weight of acrylonitrile NBR: 55 / BR: 20 / SBR: 15 / NR: 10 containing 15% by weight of acrylonitrile ZnO 5 parts by weight BR1220 30 parts by weight NR (IR) 20 parts by weight ZnO 5 parts by weight St / Ca 1.5 parts by weight ZnO 5 parts by weight SBR1502 20 parts by weight St / Ca 1.5 parts by weight VN-3 30 parts by weight St / Ca 1.5 parts by weight ZnO 5 parts by weight HAF 40 parts by weight PEG 3 parts by weight HAF 40 parts by weight St / Ca 1.5 parts by weight CZ 1.5 parts by weight DOP 5 parts by weight N280 / liquid 3 parts by weight HAF 40 parts by weight D 0.5 parts by weight CZ 1.3 parts by weight CZ 1.3 parts by weight CZ 1.5 parts by weight Sulfur 2 parts by weight D 0.43 parts by weight D 0.43 parts by weight D 0.5 parts by weight - Sulfur 1.7 parts by weight Sulfur 1.7 parts by weight Sulfur 2 parts by weight -

In the laminated rubber of Table 5, the upper rubber layer side is No. 4, and the No. And, No. 7 shows one example of the composition of the auxiliary layer. In this case, No. 7 is useful for an outsole, a bicycle, or the like.

A combination of (No. 4 + No. 6) / (No. 5 + No. 6) / (No. 5 + No. 6 + No. 7) is also useful.

Table 6 shows wet formulations and manufacturing processes that can be placed under the upper layer rubber.

Compound material Parts by weight (parts by weight) Remarks Table 5 Combination of one of No.4 to No.7 150 ~ 160 Excludes sulfur. * 1: Red iron (Fe ₂ O ₃ ) 50-100 * 1 to * 3 alone or in combination of 150 to 300 parts by weight in total.
* 1 to * 3 can be substituted or substituted for VN3 and HAF parts by weight in Table 5 up to a maximum of 300 parts by weight,
Silane-coupling is preferably used in combination. * 2: Titanium oxide (TiO ₂ ) 50-100 * 3: Zinc oxide # 3 (ZnO) 50-100 brimstone 5-20 The above blend is press-molded on a 2 mm plate at a vulcanization condition of 165 ° C to 175 ° C × 10 min and is a powder having a particle size of 2 mm or less in a crusher. In the embodiment of the present invention, the pore of the biaxial roller is adjusted to 2 mm, It is possible to easily knead the plate and the crushed pieces together with the kneaded raw material in small amounts to easily pulverize the kneaded product to 2 mm or less. Wet First layer (No. 4 to No. 7) A compound containing ebonite mixed with 100 parts by weight of rubber and 15 to 30 parts by weight of the above-mentioned crushed particles was mixed with a rubber (hereinafter referred to as Wet ).

Comparative test
(tread rubber) Abrasion (NBS)%
KSM6625: 2003 Tensile Strength (MPa)
KSM6782: 2009 Elongation (%)
KSM6782: 2009 Company A standard tire 120 ~ 200 22-28 400 to 600 Example 1 Upper layer rubber 944 35.5 480 Example 2 Upper layer rubber 1017 29.6 440 Example; Inspection Agency KIFLT
Standard Tires: Standard values for passenger cars, heavy trucks and buses are shown.

 (NBS abrasion: Abrasion%, Tensile Strength MPa, elongation%: Elongation%) of the upper layer rubber of the present invention as compared with the standard 'tire tread compounding' and the index of abrasion NBS% , Tear Strength N / m).

In particular, the abrasion resistance of the upper layer rubber of the present invention is shown to be very excellent.

Table 8 shows the interlaminar bond strengths of the tires produced according to the embodiment of the present invention.

At this time, the laminated structure is a heterogeneous rubber (standard company A company) / laminated rubber (No. 4 upper layer laminate + 5th layer laminate of Table 5) / upper layer rubber (Table 3) The results of testing the co-molded specimens by setting the UTM test speed to 100 mm / min.

test item unit result Bond strength (of the dissimilar rubber layer and laminated rubber) N / mm 3.9 (Upper layer rubber layer and laminated rubber) bond strength N / mm 3.8

The bonding strength as described above shows a very high bonding strength in view of the bonding strength of a general adhesive of 2 N / mm.

1: upper layer rubber 2: laminated rubber
10: spike 20: pedestal

Claims (7)

A rubber composition for a tire body or a shoe outsole body; and an adhesive rubber for interposing between the upper layer rubber and the dissimilar rubber, wherein the upper rubber layer is a thermosensitive rubber composition for contacting a ground surface for spike, Stacking at least one laminated rubber as a composition in a molding die; Characterized in that the rubber laminated in the molding die is simultaneously vulcanized and molded to constitute a non-slip body.
The method of claim 1,
Characterized in that said upper layer rubber is composed of a polymer blend (PB) in which acrylonitrile-butadiene rubber (NBR) is limited to a ratio of 185 ± 10 parts by weight to 100 parts by weight of a polyvinyl chloride straight resin. A method for manufacturing a non-slip body.
The method of claim 2,
Wherein the NBR is a hydrogenated NBR, a carboxylated NBR having an acrylonitrile content of 31 to 44 wt%, or a combination thereof.
The method of claim 1,
The dissimilar rubber is composed of NR (natural rubber), IR (isoprene rubber), SBR (styrene-butadiene rubber), BR (butadiene rubber) alone or a combination thereof and is made of a monomer having a conjugated double bond as a main component Wherein the diene polymer is a diene polymer or a ternary copolymer.
The method of claim 1,
Wherein the laminated rubber is selected from a homopolymer of isoprene, a homopolymer of butadiene and a copolymer of butadiene, and a polymer selected from a combination of two or more types selected from the group consisting of isoprene and butadiene. Of at least 50% by weight based on the total weight of the non-slip component.
The method according to any one of claims 1 to 5,
Wherein the vulcanizing conditions of the upper rubber and the laminated rubber are the same as the vulcanizing conditions of the different rubber.
A non-slip body manufactured by the manufacturing method according to any one of claims 1 to 5.

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