JPH08113769A - Bonding composition and laminate using bonding composition - Google Patents

Abstract

PURPOSE: To obtain a bonding composition capable of firmly vulcanizing and bonding an acrylonitrile-butadiene rubber molding to a chloroprene rubber molding by adding specific two kinds of compounds together to a chlorosulfonated polyolefin. CONSTITUTION: This composition is obtained by blending (B) 3-30 pts.wt. compound of hydrotalcites a compound of the formula [X is 0-0.5; (m) is 0-5]} and (C) 5-50 pts.wt. compound containing silicon (e.g. colloidal silica or aluminum silicate) with (A) 100 pts.wt. chlorosulfonated polyolefin (e.g. chlorosulfonated polyethylene). The composition is used by a method for dissolving the composition in, e.g. a solvent, providing a rubber cement, then coating one surface each of an acrylonitrile-butadiene rubber molding and a chloroprene rubber molding, drying the coated rubber cement, joining both the moldings and subsequently carrying out the vulcanization bonding, etc.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an adhesive composition capable of firmly adhering an acrylonitrile / butadiene rubber molding (hereinafter abbreviated as NBR molding) and a chloroprene rubber molding (hereinafter abbreviated as CR molding). The present invention relates to a laminate of an NBR molded product and a CR molded product obtained by vulcanizing and adhering the product and the adhesive composition.

[0002]

2. Description of the Related Art Acrylonitrile-butadiene rubber (hereinafter abbreviated as NBR) and chloroprene rubber (hereinafter abbreviated as CR) are special rubbers having excellent oil resistance, which may be used individually by utilizing the characteristics of the rubber. Furthermore NBR
It has been commercialized as a laminated body of CR and CR. Belts, hoses, rubber plates and the like are examples of products of this laminated body.

For example, NBR is widely used as an inner layer rubber of rubber for fuel hoses, power steering hoses, torque converter hoses, etc. because of its excellent oil resistance. On the other hand, it is not used as the outer layer of the hose because it has poor ozone resistance and weather resistance. In the manufacture of hoses, CR, which has excellent ozone resistance and weather resistance, is used as the outer rubber layer in order to cover the drawbacks of NBR.
The method of stacking R and CR has been generally adopted, and improvements have been made thereby.

[0004]

However, in such applications, NBR and CR do not have sufficient vulcanization adhesive strength, and up until now, NBR, CR, and rubber comrades that have been sufficiently vulcanized and adhered have Not manufactured.

Conventionally, hoses such as fuel hoses, power steering hoses, and torque converter hoses are called braids between the inner rubber layer and the outer rubber layer. Code, canvas form) is used. As the braided fiber, cotton, nylon, vinylon, rayon, tetron, aramid, etc. are used. In such a hose, the lack of adhesive strength between NBR and CR rubbers is caused by vulcanization between the blades and the rubbers. NBR and CR by indirectly performing vulcanization adhesion between rubbers by performing adhesion, that is, vulcanization adhesion between NBR / blade and blade / CR.
Is being manufactured.

However, this method is an indirect vulcanization bonding method between rubbers through fibers, and the bonding between the inner rubber layer and the outer rubber layer of the hose cannot be said to be sufficient. There is a problem that it cannot withstand a dynamic load such as bending fatigue and causes delamination trouble.

As described above, in the product of the laminated body of NBR and CR, strict bending fatigue resistance may be required in use, and in order to eliminate the delamination trouble between the laminated bodies caused by the insufficient bending fatigue resistance. , NB constituting the laminated body
It is required that the R molded article and the CR molded article be firmly bonded to each other, and in the market, it is strongly desired to develop a laminate having improved vulcanization adhesiveness between the NBR and the CR and having more excellent durability. Was there.

The present invention has been made in view of the above problems, and an object thereof is to bond a chlorosulfonated polyolefin composition obtained by blending a chlorosulfonated polyolefin with a hydrotalcite compound and a silicon-containing compound. By interposing it as a composition, strong vulcanization adhesion can be achieved between the NBR molded product and the CR molded product, and the production of a laminate of these molded products having a strong vulcanization adhesive force by this technique. Is possible.

[0009]

In order to solve the above-mentioned problems, the inventors of the present invention have made earnest studies to improve the vulcanization adhesiveness of NBR molded products and CR molded products, and as a result, chlorosulfonated polyolefin 100 Between the NBR molded product and the CR molded product, a chlorosulfonated polyolefin composition containing 3 to 30 parts by weight of a hydrotalcite compound and 5 to 50 parts by weight of a silicon-containing compound is used as an adhesive composition, based on parts by weight. NB only when vulcanized and bonded
The present invention has been completed by finding that strong vulcanization adhesion is exhibited between the R molded product and the CR molded product.

Hereinafter, the present invention will be described in more detail.

The adhesive composition of the present invention comprises 3 to 30 parts by weight of a hydrotalcite compound and 5 to 50 parts by weight of a silicon-containing compound with respect to 100 parts by weight of a chlorosulfonated polyolefin.

The chlorosulphonated polyolefin used in the present invention is not particularly limited as long as it is obtained by chlorinating and chlorosulphonating the polyolefin. For example, chlorine is generally contained in the molecular structure in an amount of 10 to 10 It contains 60% by weight and 0.3 to 3.0% by weight of sulfur.

The most typical chlorosulfonated polyolefin of the present invention is chlorosulfonated polyethylene obtained by using polyethylene as the polyolefin and chlorinating and chlorosulfoning this polyethylene. Examples of these chlorosulfonated polyolefins include those manufactured by Toso Corporation (trade name; TOSO-CS
M TS-430, TS-530, TS-930), D
The product manufactured by u Pont (trade name; Hypalon 40S, Hypalon 40, Hypalon 610) and the like can be mentioned. Also,
The chlorosulphonated polyolefin of the present invention may be chlorinated or chlorosulphonated using a copolymer such as an ethylene / butene-1 copolymer, an ethylene / propylene copolymer or an ethylene / vinyl acetate copolymer as the polyolefin. Chlorosulfonated ethylene butene obtained by
1-copolymer, chlorosulfonated ethylene / propylene copolymer, chlorosulfonated ethylene / vinyl acetate copolymer, etc. are also included.

The hydrotalcite-type compound used in the present invention has a chemical name of "basic magnesium aluminum hydroxide hydroxy carbonate hydrate", and for example, is represented by the following general formula (1): Is a compound represented by.

Mg _1-X Al _X (OH) ₂ (CO ₃ ) _{X / 2} · mH ₂ O (1) (In the formula, x is 0 <x ≦ 0.5, m is a number represented by 0 to 5) Examples of this hydrotalcite compound include those manufactured by Kyowa Kagaku Co., Ltd. (trade names; DHT-4A, DHT-4A).
-2, Kyoto KW-2000, KW-2100)
And the like.

The blending amount of the hydrotalcite compound is
The amount is 3 to 30 parts by weight, preferably 8 to 20 parts by weight, based on 100 parts by weight of the chlorosulfonated polyolefin. If the compounding amount of the hydrotalcite compound is less than 3 parts by weight, it cannot be said that the amount is sufficient as an acid acceptor, and there is a risk of causing a compound score, and an adhesive composition having a balanced mechanical strength. Since it does not become a thing, the adhesive strength is weak. On the other hand, if the compounding amount exceeds 30 parts by weight, the compound viscosity becomes very large, the processability and fluidity are poor, and molding may be difficult.

In the present invention, the reason for this is not clear, but in order to obtain high vulcanization adhesive strength, magnesia (MgO), which is commonly used as an acid acceptor, should not be blended. Since a sufficient effect cannot be obtained even when used in a small amount or in combination with hydrotalcite, it should be avoided.

The silicon-containing compound used in the present invention is
There is no particular limitation as long as it is a compound having silicon in the compound, and examples thereof include wet process white carbon, dry process white carbon, synthetic silicate white carbon, colloidal silica, fumed silica, Examples include hydrous aluminum silicate, aluminum silicate, kaolin clay, calcined clay, talc, wollastonite, zeolite, silica sand, and pumice powder. The compounding amount of the silicon-containing compound is 5 to 50 parts by weight, preferably 10 to 30 parts by weight, relative to 100 parts by weight of the chlorosulfonated polyolefin.
Parts by weight. If the compounding amount of the silicon-containing compound is less than 5 parts by weight, the amount of the silicon-containing compound in the bonding composition is insufficient, which is not sufficient to obtain a strong vulcanized bond. On the other hand, if the blending amount exceeds 50 parts by weight, the unvulcanized compound of the chlorosulfonated polyolefin composition becomes too hard and lacks plasticity, making processing difficult.

The adhesive composition of the present invention, as described above,
A chlorosulfonated polyolefin, a hydrotalcite compound and a silicon-containing compound are essential components, but if necessary, other reinforcing agents, fillers, vulcanization accelerators,
Compounding agents such as plasticizers, softeners, processing aids, stabilizers, and colorants may be used in combination.

The NBR molded product and CR molded product referred to in the present invention are NBR and C prepared by arbitrarily mixing various compounding chemicals with rubber.
R Indicates each unvulcanized compound. NBR refers to all of what is generally called NBR, which is composed of a copolymer rubber of acrylonitrile and butadiene, and the copolymer composition ratio and the like are not particularly limited. Also, CR
The term “all” refers to all those generally referred to as CR, which are composed of a chloroprene homopolymer and a copolymer rubber of chloroprene and a diene monomer, and the copolymer composition ratio, the modifier and the like are not particularly limited.

The laminated body is basically manufactured by NBR.
An adhesive composition composed of 3 to 30 parts by weight of a hydrotalcite compound and 5 to 50 parts by weight of a silicon-containing compound is interposed between 100 parts by weight of a chlorosulfonated polyolefin and a molded product and a CR molded product. This is a method of vulcanizing and adhering both molded products after bonding. For example, an adhesive composition of NBR molded product and CR molded product, which comprises 3 to 30 parts by weight of a hydrotalcite compound and 5 to 50 parts by weight of a silicon-containing compound, is used as a solvent with respect to 100 parts by weight of a chlorosulfonated polyolefin. This is a method in which a rubber paste is melted, the rubber paste is applied to one surface of each of the NBR molded product and the CR molded product, dried, and then both molded products are joined and then vulcanized and bonded. Further, as another production method, the adhesive composition may be used as an adhesive composition by forming it into a film or a sheet instead of using a rubber paste. This method is a method in which a film or a sheet-shaped adhesive composition is interposed between an NBR molded product and a CR molded product and then bonded and vulcanized and bonded.

[0022]

The present invention will be described in more detail by the following examples, but the present invention is not limited to these examples.

Examples 1 to 5 NBR molded products and CR molded products having the formulations shown in Table 1 were kneaded with 8 inches of open roll to prepare unvulcanized compounds. Furthermore, the adhesive composition having the composition shown in Table 2 was used (Examples 1 to 5).

The production of a laminate using these adhesive compositions and the measurement of the adhesive strength were carried out under the following conditions.

Samples for the vulcanization adhesion test were prepared beforehand.
An NBR molded product and a CR molded product each having a thickness of about 2 mm were prepared by a bun roll, and a film-like adhesive composition having a thickness of about 0.5 mm was prepared by an open roll in the same manner.

These were joined so as to form a laminate having a three-layer structure. That is, as shown in FIG. 1, the adhesive composition was used for 2 (intermediate layer), the NBR molded product was used for 1 (upper or lower layer), and the CR molded product was used for 3 (lower or upper layer). The three layers arranged in this way are sandwiched and joined together at 160 ° C x 2
A laminate (rubber plate) was obtained by press vulcanization for 0 minutes.

The adhesive strength of the laminate was measured by vulcanizing the laminate, allowing it to stand at room temperature for 1 day, and then performing a 180 ° peel test at a peel speed of 50 mm / min. Table 3 shows the vulcanization adhesive strength. From Table 3, Examples 1 to 1
The vulcanized adhesive of No. 5 had sufficient vulcanized adhesive strength.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

Comparative Example 1 Under the same conditions as in Example 1 except that the adhesive composition having the composition shown in Table 4 (the same adhesive composition as in Example 3 except that the hydrotalcite compound was not used) was used. Bonding and vulcanization adhesion were performed, and the laminated body was produced.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The results are shown in Table 5. Since the vulcanization of the adhesive composition did not proceed, a proper laminate could not be obtained.

[0033]

[Table 4]

[0034]

[Table 5]

Comparative Example 2 Except that the adhesive composition having the composition shown in Table 4 (the same adhesive composition as in Example 3 except that 5 parts by weight of magnesia was used and no hydrotalcite compound was used) was used. Then, they were joined under the same conditions as in the example and vulcanized and adhered to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The vulcanization adhesive strength is also shown in Table 5. From Table 5, the vulcanized adhesive of Comparative Example 2 did not have sufficient vulcanized adhesive strength.

Comparative Example 3 Same as Example except that the adhesive composition having the composition shown in Table 4 (the same adhesive composition as in Example 1 except that the silicon-containing compound [aluminum silicate] was not used) was used. The layers were joined under the conditions described above and vulcanized and adhered to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The vulcanization adhesive strength is also shown in Table 5. From Table 5, the vulcanized adhesive of Comparative Example 3 did not have sufficient vulcanized adhesive strength.

Comparative Example 4 The same as the Example except that the adhesive composition having the composition shown in Table 4 (the same adhesive composition as in Example 3 except that 3 parts by weight of wet-process white carbon was used) was used. Bonding was performed under the conditions, and vulcanization adhesion was performed to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The vulcanization adhesive strength is also shown in Table 5. The vulcanized adhesive of Comparative Example 4 did not have sufficient vulcanized adhesive strength.

Comparative Example 5 An adhesive composition having the composition shown in Table 4 (silicon-containing compound 55
Except that the same adhesive composition as in Example 3 was used, except that 35 parts by weight of aluminum silicate and 20 parts by weight of wet-process white carbon were used, and 15 parts by weight of the hydrotalcite compound was used. Then, they were joined under the same conditions as in the examples and vulcanized and adhered to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The results are also shown in Table 5. The plasticity of the unvulcanized compound at the time of vulcanization molding was insufficient, resulting in poor flow.

Comparative Example 6 Adhesive composition having the composition shown in Table 4 (the same adhesive composition as in Example 1 except that 2 parts by weight of the hydrotalcite compound and 10 parts by weight of aluminum silicate were used). A laminate was prepared by bonding under the same conditions as in the example except that was used and vulcanization adhesion was performed.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The results are also shown in Table 5. Since the vulcanization of the adhesive composition did not proceed, a proper laminate could not be obtained.

Comparative Example 7 The same adhesive composition as in Example 1 except that 35 parts by weight of the hydrotalcite compound was used and 10 parts by weight of wet-process white carbon was used. (Composition) was used, and bonding was performed under the same conditions as in Example, and vulcanization adhesion was performed to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The results are also shown in Table 5. The plasticity of the unvulcanized compound at the time of vulcanization molding was insufficient, resulting in poor flow.

Comparative Example 8 A NBR molded product and a CR molded product shown in Table 1 were roll-blended in a ratio of 50:50 and used as an adhesive composition. Others were the same as in the example, and vulcanization adhesion was performed to produce a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The vulcanization adhesive strength is also shown in Table 5. From Table 5, the vulcanized adhesive of Comparative Example 8 did not have sufficient vulcanized adhesive strength.

Reference Example NBR molded products and CR molded products having the formulations shown in Table 1 were joined as they were by a method without interposing an adhesive composition, and vulcanized and bonded to prepare a laminate.

A vulcanization adhesion test was conducted on this laminate under the same conditions as in the examples. The vulcanization adhesive strength is also shown in Table 5. From Table 5, it did not have sufficient vulcanization adhesive strength.

[0051]

As is clear from the above description, the adhesive composition comprising the chlorosulfonated polyolefin composition described in the present invention enables strong vulcanization adhesiveness between NBR molded products and CR molded products. As a result, there is an effect that it becomes possible to manufacture a laminated body that is sufficiently practical.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a laminate (rubber plate) showing a state in which an NBR molded product and a CR molded product are vulcanized and bonded via the bonding composition of the present invention.

[Explanation of symbols]

 1 ... upper or lower layer 2 ... intermediate layer 3 ... lower or upper layer

Claims (3)

[Claims] 1. A chlorosulfonated polyolefin 100.
A composition for bonding an acrylonitrile-butadiene rubber molded product and a chloroprene rubber molded product, characterized by comprising 3 to 30 parts by weight of a hydrotalcite compound and 5 to 50 parts by weight of a silicon-containing compound with respect to parts by weight. 2. The adhesive composition according to claim 1, wherein the hydrotalcite compound is represented by the following general formula (1). _{Mg 1-X Al X (OH} ) 2 (CO 3) X / 2 · mH 2 O (1) ( wherein, X is 0 <x ≦ 0.5, m is a number represented by 0 to 5. ) 3. A laminate of an acrylonitrile / butadiene rubber molded product and a chloroprene rubber molded product, which is obtained by vulcanizing and bonding with the bonding composition according to claim 1 or 2.