WO2005085332A1

WO2005085332A1 - Fabric-vulcanized rubber composite and process for production thereof

Info

Publication number: WO2005085332A1
Application number: PCT/JP2004/002788
Authority: WO
Inventors: Satoshi Kiso; Sadaki Mori; Yoshihiro Yabushita
Original assignee: Asics Corporation
Priority date: 2004-03-05
Filing date: 2004-03-05
Publication date: 2005-09-15
Also published as: JP4351700B2; CN101001903B; JPWO2005085332A1; CN101001903A

Abstract

A fabric-vulcanized rubber composite, obtained by impregnating a fabric with an isocyanate compound, drying the resulting fabric, impregnating the fabric with an adhesive containing a styrenic polymer, drying the resulting fabric, applying a green rubber on the fabric, and hot-pressing the obtained laminate to vulcanize the rubber and make it adhere to the fabric.

Description

Description: Combined fabric and vulcanized rubber and method for producing the same

The present invention relates to a combination of a cloth and a vulcanized rubber and a method for producing the same, and more particularly, to a method for bonding rubber / rubber sponge / fiber. Background art

Conventionally, many patents have been applied for the technology of bonding rubber and fiber, mainly from the manufacturing industry of industrial materials such as tires, belts and hoses. Basically, a composite of rubber and fiber such as tires, belts, hoses, etc. is obtained. For example, adhesion by resorcinol formalin latex (RFL) treatment or kneading-type adhesion is performed (for example, see Patent Document 1). 2).

(Patent Document 1) JP-A-54_4976

[Patent Document 2] Japanese Patent Application Laid-Open No. Hei 6-306201

RFL mainly obtains a composite of rubber and fiber in the following three steps.

(1) treating the fiber with an epoxy compound / diacid compound and heat treating at a high temperature of 200 to 250 ° C;

(2) Treat the fiber with a mixture of resorcinol-formaldehyde precondensate and rubber latex (RFL solution) and heat treat again at a high temperature of 200 to 25 Ot. (3) In unvulcanized rubber Then, the treated fiber material is embedded and vulcanized and bonded. In the kneading-type bonding, a resorcinol-formaldehyde condensate (formaldehyde generating agent that generates formaldehyde by heating), which is also used for RFL treatment, is compounded on the rubber side during the rubber processing process, and the fiber side adhesive is used. Irrespective of the presence or absence of the treatment, the unvulcanized rubber is bonded to the fiber in the vulcanization step to obtain a composite. These vulcanization bonding conditions are generally press molding by heating and pressurizing. The vulcanization time to obtain rubber-fiber composites (molded products) such as rubber belts and hoses is as long as 20 to 30 minutes. This depends on the application and largely depends on the thickness of the product obtained (about 10 mm or more). However, the main purpose is to improve the reinforcing property and rigidity in order to make a composite (molded product) using the fiber itself as a rubber reinforcing material. The conventional technology found in general tires, belts, hoses, etc. as described above is a technology for using fibers as a reinforcing material for rubber, and is completely different from the fiber-rubber bonding technology of the present invention. It is. That is, in the RFL treatment and the kneading-type adhesion in the adhesion treatment technology found in the above-mentioned tires and the like, fibers are basically embedded in rubber. On the other hand, the latter bonding is not limited to embedding fibers in rubber. In the RFL treatment, since the fiber is treated at a high temperature, deterioration and aging of the fiber are feared, and the strength of the fiber is reduced. Most also add carbon black, and the color is limited to black.

Even with the kneading-type bonding method, the problem of discoloration of fibers and rubber cannot be avoided due to the effect of formaldehyde, and it is difficult to apply it to visually exposed places. In addition, the above RFL and kneading-type bonding methods require a long time for processing methods and molding, and the equipment cost is enormous in mass production.

An object of the present invention is to provide a combination of a fabric and a vulcanized rubber which does not require high-temperature treatment, does not cause a decrease in fiber strength, and has high energy efficiency, and a method for producing the same.

An object of the present invention is to provide a combination of a cloth and a vulcanized rubber, which can complete vulcanization in a short time and has a high productivity and a required adhesive strength, and a method for producing the same.

An object of the present invention is to provide a composite of a fabric and a vulcanized rubber, which does not discolor rubber / rubber sponge / fiber because it does not use formaldehyde, and which can be made strong, and a method for producing the same. Disclosure of the invention

The present invention relates to the following inventions. 1. Impregnate the fabric with an isocyanate compound, dry it, then impregnate it with an adhesive containing a styrene-based polymer, dry it, place the unvulcanized rubber on the resulting fabric, and press it by hot pressing. A combined fabric and vulcanized rubber obtained by vulcanizing a vulcanized rubber and simultaneously adhering it to a fabric.

2. Impregnating and drying the fabric with an isocyanate compound, impregnating the obtained fabric with an adhesive containing a styrene-based polymer, and drying. Placing unvulcanized rubber on the obtained fabric and heating and pressing. And vulcanizing the unvulcanized rubber and simultaneously adhering the unvulcanized rubber to a fabric. 3. A method for producing a combined body of the above-mentioned cloth and vulcanized rubber, wherein the cloth is pre-treated with a solvent before the step of impregnating and drying the cloth with an isocyanate compound.

The bonded body of fabric and vulcanized rubber and the fabric treatment method of the present invention are fundamentally different from the prior art, and are an invention relating to a completely new rubber / rubber sponge Z fiber bonding method. In the present invention, as the fabric, synthetic fibers such as polyester fiber, polyamide fiber, acrylic fiber, polypropylene fiber, acetate fiber, glass fiber, carbon fiber, aramide fiber, and polyimide fiber; natural fibers such as cotton, silk, and hemp; In addition, woven fabrics, nonwoven fabrics, knitted fabrics obtained from other fibers, and fabrics obtained by raising the surface thereof on the other hand can be exemplified.

These fabrics are preferably pre-treated with a solvent before impregnation with the isocyanate compound. Examples of the solvent include toluene, ethyl acetate, methyl ethyl ketone, acetone and the like.

The isocyanate compound is not particularly limited as long as it has an isocyanate group. Examples thereof include phenylene diisocyanate, 1, reylene diisocyanate (TDI), xylylene diisocyanate (XDI), and triphenyl. Polyisocyanates such as methane triisocyanate (TTI), diphenyl methane diisocyanate (MDI), 1, squirrel (phenyl isocyanate), and hexamethylene diisocyanate Compounds can be exemplified.

To impregnate the fabric with the isocyanate compound, for example, A method of immersing in a liquid for impregnation can be exemplified, but the method is not limited thereto. In this case, the solid content of the isocyanate solution is preferably 0.5 to 4.2% by weight, particularly preferably 1 to 3.5% by weight. After impregnating with the isocyanate compound, it is dried at about 40 to 100 ° (preferably at about 60 to 80 ° C), and then impregnated with an adhesive containing a styrene-based polymer and dried.

Examples of the styrene polymer include styrene butene rubber (SBR) and styrene butadiene thermoplastic elastomer (SBS). The adhesive of the present invention can contain, for example, natural rubber, acrylonitrile butadiene rubber, and the like in addition to the styrene-based polymer. The adhesive of the present invention may further include a vulcanization accelerator, a plasticizer, an activator, a reinforcing material such as zinc white, sulfur, and white carbon.

The styrene content in the solid content of the adhesive of the present invention is preferably 2 to 47% by weight, particularly preferably 5 to 40% by weight. The impregnating ratio of the adhesive to the fabric is preferably 30% by weight or more, and more preferably 40 to 100% by weight, based on the weight of the fabric.

Examples of the method of impregnating the adhesive include, but are not limited to, a method of impregnating the cloth by immersing the cloth in a solution of the adhesive. After impregnating the adhesive, it is dried at about 40 to 100 ° C, preferably at about 60 to 80 ° C.

As described above, the unvulcanized rubber is placed on the fabric obtained by impregnating the adhesive containing the isocyanate compound and the styrene-based polymer (closely adhered), and then heated and pressed to vulcanize the unvulcanized rubber. At the same time, it is bonded to the fabric to obtain a combined body of the fabric and the vulcanized rubber. The heating press is performed at about 140 to 180 ° (:, preferably, at about 150 to 16 O. The heating press time is usually preferably about 3 to 10 minutes. Unvulcanized rubber Examples of the rubber component include natural rubber, isoprene rubber, styrene rubber, acrylonitrile butadiene rubber, butadiene rubber, chloroprene rubber, and butyl rubber.

The combination of the fabric and the vulcanized rubber obtained by the present invention is extremely excellent in lightness and flexibility. In addition, it is hard to be worn down and has excellent durability (wear resistance). The composite of the fabric and the vulcanized rubber of the present invention can be used, for example, for part or all of the sole of a shoe, and is preferably used as a sole having grip properties, more preferably as a sole having excellent grip properties. it can. Other than that, for example, gloves such as gloves, soccer gloves, one-point marks on clothes, one-off sapo, valet net CD support, fiber reinforced rubber (Fiber Reinforced Rub be: r), various equipment It can be used for tapes such as non-slip of the drip part, as well as floor materials. Brief Description of Drawings

FIG. 1 is a schematic diagram of the measurement of the tear peel strength of a fabric and rubber, and a graph showing the load and displacement in a tear test.

FIG. 2 is a graph showing the relationship between the amount of styrene in the adhesive and the tear peel strength.

FIG. 3 is a graph showing a relationship between an impregnation ratio of an adhesive into a fabric and a tear peel strength.

FIG. 4 is a graph showing the relationship between the solid content of the isocyanate solution and the tear strength.

FIG. 5 is a graph showing tensile strength, elongation, and tear strength of the fabric after each of the treatment of the present invention and the RFL treatment in comparison with the strength of an untreated fabric.

FIG. 6 is a schematic view showing a pattern in which a combined body of a fabric and vulcanized rubber is formed on a part of a shoe J using the method of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto.

Reference Example 1 (Preparation of isocyanate solution)

Sumitomo Bayer Urethane composed of 27% by weight of tris (phenylisocyanate) thiophene phosphate, 71% by weight of ethyl acetate, and 2% by weight of benzene with monochromatic mouth

Desmodule RFE manufactured by Co., Ltd. is diluted 1:10 with toluene and isocyanate -An isocyanate solution having a content of 2.45% by weight of the compound was prepared.

Reference Example 2 (Preparation of adhesive solution)

An adhesive consisting of natural rubber and styrene butadiene rubber (SBR) with a styrene content of 23.5% by weight and having the composition shown in Table 1 was diluted with toluene at a ratio of 5:95 to prepare an adhesive solution (1). did. The content of styrene based on the total solid content of the adhesive was 4.7% by weight.

【table 1】

() Indicates bound styrene content (% by weight)

Reference Example 3 (Preparation of unvulcanized rubber)

Unvulcanized rubber having the composition shown in Table 2 was prepared by rolling, and a 4.5 mm thick unvulcanized rubber sheet was prepared.

[Table 2]

Natural rubber 100

White carbon 40

Stearic acid 1.8

Silane coupling agent 2

Process oil 10

Activator 0.5

Zinc flower 3.5

Vulcanization aid 1.2

Anti-aging agent 1

Vulcanization accelerator B G 0.8

Vulcanization accelerator MBTS 0.15

Vulcanization accelerator MBT 0.9

Vulcanization accelerator TMTM 0.1 Example 1

A woven cloth (surface raised 50 cm x 25 cm) obtained from polyester fiber is immersed in a toluene solution for 1 minute, taken out, left at 70 ° C for 25 minutes, dried, and then added to the isocyanate solution of Reference Example 1 for 3 minutes. After immersion for 3 minutes, the product was dried at 70 ° C. for 30 minutes, then immersed in the adhesive solution of Reference Example 3 for 3 minutes, taken out, and dried at 70 ° C. for 30 minutes. The impregnation ratio of the adhesive to the fabric was 45% by weight based on the weight of the fabric. The unvulcanized rubber sheet of Reference Example 3 was placed on the obtained fabric, and heated and pressed at 155 ° C for 5 minutes to vulcanize the unvulcanized rubber and simultaneously adhere to the fabric to vulcanize the fabric. A rubber conjugate was obtained. The tear peel strength between the rubber and the fabric of the obtained composite was measured by the following method. As a result, a tearing-off strength of 5.4 kgf · cm was obtained. Table 3 shows the results. Measuring method

Tensile testing machine: STROGRAPH VI-B manufactured by Toyo Seiki Seisaku-sho, Ltd.

Tear test method: At a crosshead speed of 5 Omm / min, rubber was chucked at one end and the fabric was chucked at one end, and the load and displacement were measured under the above conditions. The thickness of the rubber that checks one end was 4 mm and the width was 2 cm.

Tear test strength: From the load and displacement obtained in the above test, the peel energy per unit width of the chucked rubber E 1 (FIG. 1) was taken as the tear peel strength between the fabric and rubber. Examples 2 to 5 and Comparative Example 1

Styrene butadiene rubber (SBR) with a styrene content of 23.5% by weight, 46.0% by weight, and 65.0% by weight, and a composition shown in Table 3 mainly composed of natural rubber In the same manner as in Example 1 except that the adhesive consisting of

Table 3 and FIG. 2 show the results of measuring the tear-peeling strength between the rubber and the fabric of the obtained composite in the same manner as in Example 1. [Table 3]

() Indicates the amount of bound styrene (% by weight) Examples 6 to 8 and Comparative Example 2

When preparing the adhesive solution of Reference Example 2, the ratio of toluene was changed so that the impregnation ratio of the adhesive into the fabric was 20% by weight (Comparative Example 2), 35% by weight, 80% by weight, and 130% by weight. A combined body of the cloth and the vulcanized rubber was obtained in the same manner as in Example 1 except that (Examples 6 to 8) were used.

FIG. 3 shows the result of measuring the tear-peeling strength between the rubber and the fabric of the obtained combined body in the same manner as in Example 1.

Examples 9 to 12 and Comparative Examples 3 to 4

When preparing the isocyanate solution of Reference Example 1, the concentration of the solids in the isocyanate solution was changed to 1.2%, 2.0%, 2.5%, and 3.7% by weight by changing the ratio of toluene. Examples 9 to 12), 0% by weight, and 4.5% by weight (Comparative Examples 3 to 4) were performed in the same manner as in Example 1 to obtain a conjugate of a cloth and a vulcanized rubber. FIG. 4 shows the results of measuring the tear-peeling strength between the rubber and the fabric of the obtained combined body in the same manner as in Example 1.

Comparative Example 5

A bonded body of a vulcanized rubber and a fabric was obtained in the same manner as in Example 1 except that the fabric was immersed in an isocyanate solution and dried without using an adhesive in Example 1. The tear strength between the rubber and the fabric of the obtained conjugate was 1.6 kgf · cm. Test example 1

A comparison of the peel strength between the bonding method of the present invention and general RFL treatment was made as follows.

(1) Adhesive of the present invention and processing conditions

The cloth was impregnated with the adhesive at a ratio of 30% by weight based on the weight of the cloth, and the uncured rubber and the cloth were heated and pressed at 160 ° C for 6 minutes, except that the cloth was heated in the same manner as in Example 1. And a composite of vulcanized rubber. The tear strength between the rubber and the fabric of the obtained composite was 6.5 kgf · cm. Also, the color of the fabric was improved to a light gray color rather than the original dark gray color.

(2) RFL processing

The fibers were washed and treated with the isocyanate compound in the same manner as in Example 1, heat-treated at 250 ° C for 1 minute, and then treated with a mixed solution (RFL) of the initial compound of resorcinol-formaldehyde and rubber latex (250 ° C). CX was heat-treated for 1 minute, and the unvulcanized rubber and the fabric were hot-pressed at 160 ° C. for 6 minutes to obtain a combined fabric and vulcanized rubber. The tear strength between the rubber and the fabric of the obtained bonded article was 2.7 kgf · cm. Further, the color of the fabric was changed from the original dark gray color to brown.

(3) Measurement of fiber strength change

Fig. 5 shows the tensile strength, elongation, and tear strength of the fiber after the treatments (1) and (2), together with the strength of the untreated fiber. Tensile strength, elongation, and tear strength were measured according to JIS L1018, respectively.

Test example 2 A vulcanized rubber was placed in a pattern on the polyester cloth impregnated with the adhesive of Example 3 as shown in FIG. 6 (c), and a combined body of the cloth and the vulcanized rubber was obtained in the same manner as in Example 1. . As shown in Fig. 6 (d), the perimeter is cut into the desired shape using a punching die as shown in Fig. 6 (d), and glued to the forefoot of the shoe tool shown in Fig. 6 (b) with a urethane adhesive. (a) was obtained. Industrial applicability

The method of the present invention does not require high-temperature treatment, does not cause a decrease in fiber strength, and can provide a combination of a vulcanized rubber and a fabric with high energy efficiency. Further, in the present invention, vulcanization is completed in a short time, the productivity is high, and a bonded body of a cloth and a vulcanized rubber having a necessary adhesive strength can be obtained.

In addition, since formaldehyde is not used in the present invention, a rubber / rubber sponge sponge / fiber has no discoloration, and it is possible to obtain a composite of a fabric and a vulcanized rubber which can be made strong.

Claims

The scope of the claims

1. Impregnate the fabric with an isocyanate compound, dry it, then impregnate it with an adhesive containing a styrene polymer, dry it, place the unvulcanized rubber on the resulting fabric, and press it by heating and pressing. A combined fabric and vulcanized rubber obtained by vulcanizing a vulcanized rubber and simultaneously adhering it to a fabric.

2. Woven fabric, knitted fabric, non-woven fabric whose fabric is obtained from polyester fiber, polyamide fiber, acrylic fiber, polypropylene fiber, acetate fiber, glass fiber, carbon fiber, aramide fiber, polyimide fiber, cotton, silk, hemp, etc. The combined product of the cloth according to claim 1 and a vulcanized rubber.

3. The combined fabric and vulcanized rubber according to claim 1, wherein the rubber is natural rubber, isoprene rubber, styrene butadiene rubber, acrylonitrile butadiene rubber, butadiene rubber, chloroprene rubber, or butyl rubber.

4. The method according to claim 1, wherein the styrene content in the solid content of the adhesive is 2 to 47% by weight, and the impregnation ratio of the adhesive to the fabric is 30% by weight or more based on the weight of the fabric. Combination of the cloth and vulcanized rubber described in 1.

5. The combination of the cloth and the vulcanized rubber according to claim 1, which is used as at least a part of a sole of a shoe.

6. Impregnating and drying the fabric with an isocyanate compound, impregnating the obtained fabric with an adhesive containing a styrene-based polymer, and drying. Placing unvulcanized rubber on the obtained fabric and heat-pressing. And vulcanizing the unvulcanized rubber and simultaneously adhering the unvulcanized rubber to a fabric.

7. The fabric according to claim 6, wherein the fabric is immersed in an isocyanate solution to impregnate the fabric with an isocyanate compound, wherein the solid content of the isocyanate solution is 0.5 to 4.2% by weight. Of vulcanized rubber and composite.

8. The method according to claim 6, wherein the cloth is pretreated with a solvent before the step of impregnating and drying the cloth with the isocyanate compound.