JPH064751B2 - Thermoplastic rubber composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a rubber composition as an impact resistance imparting component for engineering plastics.

(Prior Art and Problems) For improving the impact resistance of thermoplastic engineering plastics, a technique of blending these various rubbers individually or in a plurality thereof is well known and widely used. At the same time, the rubber compounded for this purpose is usually compounded because it has been modified by various chemical or physical methods. For example, JP-A-60-94407 and U.S. Pat. No. 4,174,358 are applicable to polyesters and polyamides.

However, such a modified rubber composition has the drawbacks of low weather resistance, causing discoloration and deterioration of physical properties immediately, and poor heat resistance. Further, the presence of gel, which is considered to be caused by the nonuniform reaction during the modification, is one of the drawbacks of these modified rubbers.

On the other hand, a polyoctenylene resin is known as a rubber that does not have gel and has good weather resistance and heat resistance, but when blended with various engineering plastics, the effect of improving impact resistance was insufficient.

Therefore, the inventors of the present invention have arrived at the present invention as a result of earnestly studying to develop a rubber composition having impact resistance imparting excellent weather resistance and heat resistance and having no gel.

(Means for Solving the Problems) That is, the present invention relates to polyoctenylene resin with respect to α, β-
An unsaturated carboxylic acid or its derivative is added in an amount of 0.005 to 1 mol per 1 mol of the double bond of the polyoctenylene resin, and a polymerization inhibitor is used as an α, β-unsaturated carboxylic acid or its derivative 1.
It is a thermoplastic rubber composition prepared by mixing 0.1 to 10 parts by weight with respect to 00 parts by weight.

The polyoctenylene resin used in the present invention is obtained by polymerizing cyclooctene, has one double bond per 8 carbon atoms, and needs to have a molecular weight of 10,000 or more. 50% or more, preferably 6
The crystallinity is preferably 0% or more and 10% or more. The polyoctenylene resin has a melting point of 40 ° C or higher, preferably 50 ° C to 60 ° C, and a glass transition point of -75 ° C to -30 ° C. Various methods can be adopted as a method for synthesizing cyclooctene, which is a base material constituting the polyoctenylene resin, but, for example, after dimerizing butadiene, one of two remaining double bonds is hydrogenated. Is obtained by

Examples of the α, β-unsaturated carboxylic acid or its derivative used in the present invention include monocarboxylic acids such as acrylic acid and methacrylic acid, dicarboxylic acids such as maleic acid and fumaric acid, or their anhydrides and esterifiers. be able to.

Further, the polymerization inhibitor used for preventing gelation in the present invention may be one generally used as an inhibitor or inhibitor of radical polymerization, for example, hydroquinone, methylhydroquinone, hydroquinone such as hydroquinone monomethyl ether, P-benzoquinone,
Benzoquinones such as 2,5-dichloro-P-benzoquinone, 2,6-dichloro-P-benzoquinone and 2,3,5,6-tetrachloro-P-benzoquinone (chloranil), nitrobenzene, m-dinitrobenzene, 1 , 3,
Aromatic nitro compounds such as 5-trinitrobenzene, picric acid-P-nitrotoluene and 1,3,5-trinitrotoluene, catechols such as P-tert-butylcatechol, dithiobenzoyl disulfide, furfrillinodenmalone nitrile, P -Phenyldiamine, sulfur, copper (II) chloride, etc., and stable radicals such as diphenylpicrylhydrazyl (DPPH), di-P
-Fluorophenylamine, tri-P-nitrophenylmethyl and the like can be mentioned.

In the present invention, α, β for polyoctenylene resin
The amount of unsaturated carboxylic acid or its derivative added is 0.005 to 1 mol of double bond in the polyoctenylene resin.
It is necessary to add 1 mol, and if it is 0.005 mol or less, the effect of improving impact resistance when blended with an engineering plastic is insufficient, and if it is 1 mol or more, gel in the composition increases.

Further, in the thermoplastic rubber composition of the present invention, the addition amount of the polymerization inhibitor needs to be 0.1 to 10 parts by weight based on 100 parts by weight of the α, β-unsaturated carboxylic acid or its derivative. is there. If the amount is less than 0.1 parts by weight, the polyoctenylene resin will gel during compounding and the workability will decrease. If the amount is more than 10 parts by weight, the polyoctenylene resin will not be sufficiently modified and the impact resistance when mixed with engineering plastics will be poor. Not improved enough.

In addition, α, β to the polyoctenylene resin in the present invention
-As a method of blending the unsaturated carboxylic acid or its derivative and the polymerization inhibitor, various methods such as a melt blending method using an extruder or a kneader, and a method of blending in a solution can be adopted. In this case, a small amount of peroxide can be used together.

The composition of the present invention includes the polyoctenylene resin, α,
In addition to the essential components of the β-unsaturated carboxylic acid or its derivative and the polymerization inhibitor, if necessary, an antioxidant, an ultraviolet absorber, a heat stabilizer, a nucleating agent, a plasticizer, an antistatic agent,
It is also possible to mix a flame retardant, an inorganic filler and the like.

The thermoplastic rubber composition of the present invention is melt-kneaded with other engineering plastics by various conventionally known methods, and then molded into an arbitrary shape by a usual melt molding method, and used for a wide range of applications.

(Examples) Next, the present invention will be specifically described with reference to Examples, but these are for explaining the present invention and do not limit the present invention.

Examples 1 to 5 Polyoctenylene resin (VLSTENAME manufactured by hls
R8012) was dissolved in xylene, and maleic anhydride and hydroquinone in the amounts shown in Table 1 and benzoyl peroxide in an amount of 1% of the polyoctenylene resin were added, and the mixture was stirred at 120 ° C. for 2 hours to carry out the reaction. It was The reaction product was poured into a large amount of acetone, and the precipitate was collected by filtration. Using this precipitate, a tensile test piece was molded by using a usual injection molding machine and left in a weather O meter for 500 hours. Using this sample, a tensile test was carried out with a tensile tester, and the presence or absence of deterioration of physical properties was also examined. Separately from this, pellets were used, and the film was extruded by flow-flow molding using a film extruder, and the presence or absence of gel was examined by visually observing the melted portion. The results are also shown in Table 1.

Example 6 Polyoctenylene resin (made by hls VESTENAME
R8012) was mixed with maleic anhydride as shown in Table 1, melt-blended with an ordinary extruder, and then pelletized with a pelletizer. Using these pellets, a tensile test piece was molded using a normal injection molding machine, and changes in tensile properties over time and the presence or absence of gel were examined. The results are also shown in Table 1.

Example 7 A tensile test piece was prepared in the same manner as in Example 6 except that fumaric acid was used instead of maleic anhydride. The change in tensile properties of this product with time and the presence or absence of gel were examined. The results are also shown in Table 1.

Example 8 A tensile test piece was prepared in the same manner as in Example 2 except that oleic acid was used instead of maleic anhydride and chloranil was used instead of hydroquinone. The change in tensile properties of this product with time and the presence or absence of gel were examined. The results are also shown in Table 1.

Comparative Example 1 A tensile test piece was prepared in the same manner as in Example 1 except that maleic anhydride and hydroquinone were not used. Table 1 shows the results of examining the change over time in the tensile properties of this material and the presence or absence of gel.

Comparative Example 2 In Example 1, the addition amount of maleic anhydride was 0.50 mol per mol of double bond of polyoctenylene resin,
Tensile test pieces were prepared in exactly the same manner as in Example 1 except that hydroquinone was not used. Table 1 shows the results of examining the change over time in the tensile properties of this material and the presence or absence of gel.

Comparative Example 3 A tensile test piece was prepared in the same manner as in Example 6 except that the amount of methylhydroquinone added was 0.05 part by weight. Table 1 shows the results of examining the change over time in tensile properties and the presence or absence of gel.

Claims (1)

[Claims] 1. A polyoctenylene resin containing 0.005 to 1 mol of an α, β-unsaturated carboxylic acid or derivative thereof per 1 mol of a double bond of the polyoctenylene resin, and an α, β-unsaturated carboxylic acid as a polymerization inhibitor. Acid or its derivative 10
A thermoplastic rubber composition comprising 0.1 to 10 parts by weight based on 0 parts by weight.