JPH06207110A - Adhesive thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To provide excellent in oil resistance, impact resistance, sliding property, gas barrier property and flexibility by dispersing the particles of a cross- linked rubber in specific mixed polymers. CONSTITUTION:The elastomer is characterized by dispersing (A) the particles of a cross-linked rubber preferably in an amount of 50-150vol.pts. in 100vol.pts of (B) a thermoplastic resin or elastomer partially modified with maleic anhydride or mixed polymers comprising the modified resin or elastomer preferably in an amount of 100-30vol.% and (C) a non-modified thermoplastic resin of elastomer preferably in an amount of 0-70vol.%.

Description

Detailed Description of the Invention

[0001]

The present invention has rubber-like physical properties,
The present invention relates to a thermoplastic elastomer having excellent adhesion to different polar materials such as nylon and polyurethane.

[0002]

2. Description of the Related Art Conventionally, SEBS modified with maleic anhydride has been used as an adhesive thermoplastic elastomer having physical properties closest to those of rubber. Originally, SEBS is a thermoplastic elastomer with excellent flexibility and elasticity.
By partially modifying EBS with maleic anhydride, the maleic anhydride incorporated into the molecular structure chemically bonds with a functional group in a polar resin such as nylon or polyurethane, that is, adhesion with the polar resin. Is made possible.

[0003]

However, the modified SEB
In terms of physical properties, S has a drawback in that it has a large permanent deformation during heating and is very expensive.

The present invention has been made in order to solve such a problem, has excellent flexibility and elasticity, has a small permanent deformation during heating, and has a more rubber-like physical property, and is inexpensive. Another object is to provide an adhesive thermoplastic elastomer that is much cheaper than conventional ones.

[0005]

The present invention is directed to a thermoplastic resin or elastomer partially modified with maleic anhydride.
Alternatively, a mixed polymer of the modified resin or elastomer and a non-modified thermoplastic resin or elastomer is used as a base, and a rubber crosslinked by the method (i) or (ii) shown below is used therein. It is obtained by dispersing particles substantially uniformly. (I) Dynamic vulcanization is performed. That is, when the above-mentioned base polymer and the uncrosslinked rubber are kneaded while being heated, the rubber having a higher viscosity becomes particles and is dispersed in the base polymer. While further heating, a crosslinking agent is added thereto and mixed to crosslink the rubber particles in the base polymer. (Ii) The pre-crosslinked rubber is finely pulverized into particles, and the rubber particles are added to and mixed with the base polymer without heating to disperse the rubber particles in the base polymer. The composition ratio of the base polymer is preferably 100 to 30 vol% for the modified resin or elastomer, and about 0 to 70 vol% for the unmodified resin or elastomer. When a resin is used as the base polymer, the compounding amount is appropriately adjusted as long as the present invention can finally be a flexible elastic body. On the other hand, the ratio of the added rubber is preferably about 50 to 150 parts by volume with respect to 100 parts by volume of the base polymer, and the particle size is appropriately adjusted to about 1 to several μm. In the rubber particle dispersion method described above, in order to reduce the cost and simplify the manufacturing process, (i)
Is preferably selected.

[0006]

In the present invention, maleic anhydride is incorporated into the molecular structure of the base polymer, thereby
It chemically bonds with the functional groups of a polar resin such as nylon or polyurethane, that is, enables adhesion with the polar resin. The polarity of the maleic anhydride-modified thermoplastic polymer is generally small, but as a typical method for adhering a nonpolar polymer having no affinity to the polar polymer, a method of subjecting the surface of the nonpolar polymer to a halogenation treatment is generally used. However, to that end, the types of non-polar polymers used were limited to those with unsaturated bonds which allowed halogenation. However, in the case of the present invention, regardless of the polarity of the base polymer, adhesion with a polar resin can be obtained without halogenation treatment, and a film of the polar resin can be easily formed on the surface of the elastomer according to the present invention to improve oil resistance. And wear resistance, slidability, and gas barrier properties can be improved.

In addition, the present invention contains fine rubber particles inside, so that while maintaining excellent moldability as a thermoplastic polymer, it is excellent in flexibility and elasticity, and has a small permanent deformation upon heating. That is, it has physical properties very similar to rubber. Moreover, as the rubber particles to be used, low-priced non-polar rubber (NR, IR, BR, SBR, EPD) is used.
M, IIR, etc.) makes the present invention much cheaper in composition than conventional products with only modified SEBS.

Examples of the present invention will be described below, but the invention is not limited thereto.

[Example 1] In this example, a thermoplastic polymer in which cross-linked EPDM particles are almost uniformly dispersed in a mixed polymer of polypropylene partially modified with maleic anhydride and unmodified SEBS It is an elastomer.
This example is made according to the formulation and method shown below.

[0010]

[Table 1]

[0011]

[Table 2]

Based on the formulation shown in Table 1, first, an uncrosslinked EPDM (EPT3054, manufactured by Mitsui Petrochemical Co., Ltd.) was used.
While kneading with an open roll heated to 80 ° C, paraffinic process oil (Diana Process Oil PW90 manufactured by Idemitsu Petrochemical Co., Ltd.) as a softening agent and carbon black (Show Black O manufactured by Showa Denko) as a reinforcing agent.
Was added and mixed, and further, modified polypropylene (Mitsui Petrochemical Co., Admer OF305) and SEBS (Asahi Kasei Co., Tuftec H1052) were added and kneaded for 10 minutes. It will be in a state of being dispersed in the modified polypropylene / SEBS mixed polymer. While further heating and maintaining the same temperature, various vulcanizing agents shown in Table 2 are added and mixed for 10 minutes to crosslink the EPDM particles.

Example 2 In this example, a thermoplastic polymer was prepared in which particles of crosslinked EPDM were almost uniformly dispersed in a mixed polymer of polypropylene partially modified with maleic anhydride and unmodified polypropylene. It is an elastomer. This example is made according to the formulation and method shown below.

[0014]

[Table 3]

[0015]

[Table 4]

Based on the formulation shown in Table 3, first, uncrosslinked EPDM (the same as in the first embodiment) was heated to 180 ° C.
While kneading with a heated open roll, paraffinic process oil (similar to the first embodiment) as a softening agent and carbon black (similar to the first embodiment) as a reinforcing agent are added and mixed. In addition, modified polypropylene (Mitsui Petrochemical, Admer OF305)
And polypropylene (Sumitomo Chemical Co., Nobren W50
Add 1) and knead for 10 minutes to obtain a highly viscous EPDM
Become particles and become dispersed in the modified polypropylene / polypropylene mixed polymer. While further heating and maintaining the same temperature, various vulcanizing agents shown in Table 4 are added and mixed for 10 minutes to crosslink the EPDM particles.

Example 3 In this example, a thermoplastic polymer was prepared in which particles of crosslinked IIR were dispersed almost uniformly in a mixed polymer composed of polyethylene partially modified with maleic anhydride and unmodified SEBS. It is an elastomer. This example is made according to the formulation and method shown below.

[0018]

[Table 5]

[0019]

[Table 6]

Based on the formulation shown in Table 5, first, uncrosslinked IIR (manufactured by Bayer, Polycerbutyl 402) was added to 1 part.
While kneading with an open roll heated to 80 ° C., paraffinic process oil (similar to the first example) as a softening agent and carbon black (similar to the first example) as a reinforcing agent were added. And mix, and then
Modified polyethylene (Mitsui Petrochemical, Admer HB0
When 30) and SEBS (the same as in the first embodiment) are added and kneaded for 10 minutes, the high-viscosity IIR becomes particles and is dispersed in the modified polyethylene / SEBS mixed polymer. While further heating and maintaining the same temperature, various vulcanizing agents shown in Table 6 are added and mixed for 10 minutes to crosslink the IIR particles.

Example 3 This example is a thermoplastic elastomer in which particles of crosslinked SBR are dispersed almost uniformly in SEBS partially modified with maleic anhydride. This example is made according to the formulation and method shown below.

[0022]

[Table 7]

[0023]

[Table 8]

Based on the formulation shown in Table 7, first, uncrosslinked SBR (Tufden 2000, manufactured by Asahi Kasei Co.) was heated to 180 ° C.
While kneading with an open roll heated to, add naphthene-based process oil (Diana Process Oil NS24, manufactured by Idemitsu Petrochemical Co., Ltd.) as a softening agent, and carbon black (the same as in the first embodiment) as a reinforcing agent. After mixing and further adding modified SEBS (Tuftec M1943, manufactured by Asahi Kasei Co., Ltd.) and kneading for 10 minutes, the highly viscous SBR becomes particles and is dispersed in the modified SEBS. There, while heating and holding at the same temperature,
Add the vulcanizing agents shown in Table 8 and mix for 10 minutes.
Crosslink the SBR particles.

[0025]

INDUSTRIAL APPLICABILITY The present invention is a thermoplastic elastomer in which maleic anhydride incorporated in the molecular structure imparts adhesiveness to a polar resin such as nylon or polyurethane. It is possible to easily form a film of a polar resin on the surface of the elastomer according to the present invention, thereby improving oil resistance, abrasion resistance, slidability, and gas barrier property, and expanding applications. In addition, the present invention has very rubber-like physical properties while maintaining excellent moldability, is rich in flexibility and elasticity, and is a conventional modified SE.
Permanent deformation during heating is small compared to BS. Further, the present invention is excellent in that the price is very low compared to the conventional product, because inexpensive rubber is mixed in an amount of about 50 to 150 parts by volume with respect to 100 parts by volume of the thermoplastic polymer as the base. The effect can be obtained.

Claims (1)

[Claims] 1. A crosslinked rubber in a thermoplastic resin or elastomer partially modified with maleic anhydride, or a mixed polymer of the modified resin or elastomer and the unmodified thermoplastic resin or elastomer. An adhesive thermoplastic elastomer in which particles are dispersed.