JP3044255B2 - Thermoplastic rubber composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic rubber composition. The thermoplastic rubber composition of the present invention is molded and processed in a resin processing field, a rubber processing field, and the like, and is used as an electric wire, cable, mat, hose, roofing, and the like.

(Prior art) Conventionally, a thermoplastic rubber composition comprising a rubber containing a gel component and a thermoplastic resin obtained by dynamically heat-treating and vulcanizing the rubber while kneading the rubber and the thermoplastic resin has a thermoplastic property. Since it has rubber elasticity, it is molded at a high temperature by utilizing its thermoplasticity and used within a temperature range having rubber elasticity. In general, a thermoplastic rubber composition has the advantages that it is easy to flow at high temperatures, is easy to mold, and has a short molding time. Also, in the molding process of the rubber composition, a vulcanization step is required, but in the case of a thermoplastic rubber composition, such is not necessary.Because it is superior to the rubber composition in terms of energy consumption or labor costs, In recent years, it has been widely used in the resin field and rubber field.

In recent years, chlorinated polyethylene and / or chlorosulfonated polyethylene and a thermoplastic resin have been subjected to dynamic heat treatment and vulcanization to be used as a thermoplastic rubber. However, to contain the gel component, chlorinated polyethylene obtained by dynamic heat treatment using a conventionally used system of a dehydrochlorination scavenger and a vulcanizing agent for rubber and / or a vulcanization accelerator for rubber, and And / or a thermoplastic rubber composition comprising chlorosulfonated polyethylene and a thermoplastic resin,
In molding at a high temperature of not less than ℃, the fluidity is extremely poor. For example, in molding with an injection molding machine, the molding cycle is slow, and products with complicated shapes cannot be molded,
Extrusion by an extruder has disadvantages such as a low extrusion speed and the inability to mold a product having a complicated shape. In order to put a thermoplastic rubber composition comprising a chlorinated polyethylene and / or chlorosulfonated polyethylene containing a gel component and a thermoplastic resin into practical use, it is necessary to solve the above-mentioned problems.

(Problems to be Solved by the Invention) The present inventors have assiduously studied to solve the above-mentioned problems, and as a result, provide a thermoplastic rubber composition in which flow characteristics in molding processing have been solved.

(Means for Solving the Problems) The present invention provides a chlorinated polyethylene and / or chlorosulfonated polyethylene containing a gel component, a thermoplastic resin, a dehydrochlorination scavenger, a mercaptotriazine-based compound,
The present invention relates to a thermoplastic rubber composition comprising an epoxy compound. The thermoplastic rubber composition provided by the present invention has extremely excellent flow characteristics in molding at high temperatures and can be put to practical use.

 Hereinafter, the present invention will be described in detail.

The chlorinated polyethylene used in the present invention includes polyethylene, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-ethyl acrylate copolymer, ethylene-acryl Powders or particles of an acid methyl copolymer or the like are suspended in water, or dissolved in an inert organic solvent such as carbon tetrachloride and blown with chlorine gas to introduce chlorine to form a rubber. The amount of chlorine is not particularly limited as long as the chlorinated polyethylene is in a rubber state, but 15 to 55% by weight of the chlorinated polyethylene is in a rubber state.

The chlorosulfonated polyethylene used in the present invention is obtained by dissolving the polymer in an inert organic solvent such as carbon tetrachloride, blowing in chlorine gas and chlorinating, and then adding and reacting chlorosulfonyl. A chlorosulfonyl group is introduced into the rubber, or chlorine and a chlorosulfonyl group are introduced by chlorosulfonyl to form a rubber.
The amount of chlorine is not particularly limited as long as the chlorosulfonated polyethylene is rubbery as in the case of the chlorinated polyethylene.
~ 55% by weight of the chlorosulfonated polyethylene is in rubbery form. The production methods of chlorinated polyethylene and chlorosulfonated polyethylene have been described above, but the chlorinated polyethylene and / or chlorosulfonated polyethylene used in the present invention is not limited to these production methods.

In the present invention, the chlorinated polyethylene and / or chlorosulfonated polyethylene containing a gel component is:
Chlorinated polyethylene and / or chlorosulfonated polyethylene obtained by vulcanizing chlorinated polyethylene and / or chlorosulfonated polyethylene by dynamic heat treatment in a kneader. The gel component referred to in the present invention refers to a residue obtained by extracting a benzene unextracted into benzene from a residue measured by a Harris basket made of a 100-mesh stainless steel wire mesh in accordance with JIS K 6388 of the obtained thermoplastic rubber composition. Residue excluding a certain amount of thermoplastic resin. And the amount of the gel component in the thermoplastic rubber composition is 20% by weight or more,
Preferably at from 40 to 60% by weight, the thermoplastic rubber composition exhibits very good flowability. If the amount is less than 20% by weight, the mechanical properties of the thermoplastic rubber composition such as compression set and permanent elongation are inferior.

The thermoplastic resin used in the present invention is a resin that melts at a high temperature of 100 ° C. or higher, for example, polyethylene,
Ethylene vinyl acetate copolymer, polypropylene, polystyrene, polyamide, thermoplastic polyurethane, polycarbonate, phenoxy resin, polymethyl methacrylate, methyl methacrylate / styrene copolymer, fluoro resin, polyvinyl butyral, polyvinyl formal, polyvinylidene chloride, chlorine Polyether, styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, polyacetal and the like. These can be used alone or in combination. The amount to be used is 5 to 50 parts by weight, preferably 10 to 40 parts by weight of a thermoplastic resin per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene. If the amount is less than 5 parts by weight, the resulting thermoplastic rubber composition has poor fluidity and is difficult to mold. Further, when the addition exceeds 50 parts by weight, the resulting molded product is hard, does not exhibit rubber elasticity, and lacks practicality.

The dehydrochloric acid scavenger used in the present invention is an agent for scavenging hydrochloric acid generated when chlorinated polyethylene and / or chlorosulfonated polyethylene is dynamically heat-treated and vulcanized to contain a gel component. As the dehydrochlorination scavenger, metal oxides, metal lead compounds, metal hydroxides, fatty acid metal soaps such as magnesium oxide, calcium oxide,
Examples include zinc oxide, lead monoxide, lead tetroxide, tribasic lead sulfate, dibasic lead phosphite, calcium hydroxide, sodium stearate, magnesium stearate, calcium stearate and the like. These can be used alone or in combination. The amount used is 0.5 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene. The dynamic heat treatment referred to in the present invention refers to a kneader for resin or rubber, for example, a roll kneader, a Banbury mixer, a double-arm kneader, a screw-type kneader, a rotor-type continuous kneader, or the like. Refers to vulcanization while flowing a chlorinated polyethylene and / or a chlorosulfonated polyethylene in a kneader to form a gel component. The temperature of the dynamic heat treatment is preferably from 140 to 250C.

The mercaptotriazine-based compound used in the present invention is a mercaptotriazine-based compound having two or more thiol groups generally used as a vulcanizing agent for chlorine-based rubber, for example, 1,3,5-trithiocyanur Acid, 1-methoxy-3,5-dimercaptotriazine, 1-phenylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-dimercaptotriazine, 1-dibutylamino-3,5-dimercapto Triazine, 1-hexylamino-3,5-dimercaptotriazine, 1-diethylamino-3,5-dimercaptotriazine and the like. These can be used alone or in combination. The amount used is 0.1 parts per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene.
-10 parts by weight, preferably 1-5 parts by weight. 0.
If the amount is less than 1 part by weight, the amount of the gel component in the obtained thermoplastic rubber composition does not reach 20% by weight, and the mechanical properties of the thermoplastic rubber composition such as compression set and elongation are inferior.

In the present invention, vulcanizing agents for chlorine rubber other than mercaptotriazine compounds having two or more thiol groups used as vulcanizing agents for chlorine rubber have no effect.

The epoxy compound used in the present invention is a hydroxyl group,
Alternatively, a compound having one or more epoxy groups in a compound formed by reacting a compound having an active group such as a carboxyl group or an amino group with epichlorohydrin, and an epoxy compound formed by reacting bisphenol A with epichlorohydrin; Epoxidized novolak compound, epoxidized cresol compound, epoxidized alcohol compound, epoxidized methacrylic acid compound produced by the reaction of
It is represented by an epoxidized phenyldiamine compound. These can be used alone or in combination. The amount used is 0.1 to 20 parts by weight per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene,
Preferably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight is used. If the amount is less than 0.1 part by weight, the obtained thermoplastic rubber composition has poor flow characteristics and cannot be used practically. If the amount is more than 20 parts by weight, the resulting thermoplastic rubber composition is hard and does not exhibit rubber elasticity, which is not preferable.

The method for obtaining the thermoplastic rubber of the present invention is not particularly limited, but using the above-described roll kneader, Banbury mixer, double-arm kneader, screw-type kneader, rotor-type continuous kneader, or the like. Chlorosulfonated polyethylene, a thermoplastic resin, a dehydrochlorination scavenger, and a mercaptotriazine compound are kneaded, followed by dynamic heat treatment, and then an epoxy compound is preferably added and mixed. In the thermoplastic rubber composition of the present invention, a compounding agent for rubber or resin can be added in the process of obtaining the composition or after obtaining the composition. For example, these additives include vulcanization accelerators, vulcanization activators, plasticizers, softeners, antioxidants, ultraviolet absorbers, carbon black, or white fillers such as titanium oxide, calcium carbonate, talc and clay. , Foaming agents, lubricants, slip agents, antistatic agents, coloring agents and the like. For molding the thermoplastic rubber composition of the present invention, for example, an extrusion molding machine, an injection molding machine, a calender roll, a press molding machine, a blow molding machine or a vacuum molding machine is used.

(Examples) The present invention will be described with reference to the following examples, but the present invention is not limited to these examples.

Examples 1 to 4 and Comparative Examples 1 to 4 Table 1 shows the formulations of the thermoplastic rubber compositions used in Examples and Comparative Examples.

Example 1 uses the formulation shown in Table 1, while chlorosulfonated polyethylene, magnesium oxide, DOP and 1,3,5-trithiocyanuric acid at a temperature of 50 ° C.
Kneading with a roll to obtain a rubber kneaded material, while 140 ° C
Nocrack NS-6 manufactured by Ouchi Shinko Chemical Industry Co., Ltd. was added to polyethylene as an antioxidant with a roll of No. 1 and kneaded to obtain a thermoplastic resin kneaded product. Next, using a Brabender plastic coder roller mixer type, the obtained rubber kneaded material and thermoplastic resin kneaded material are put into a chamber at a set temperature of 140 ° C., and the rubber kneaded material is mixed with the rubber kneaded material using a roller mixer 100 RPM. Was melt-dispersed and then subjected to a dynamic heat treatment, followed by adding and kneading Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. as an epoxy compound to obtain a thermoplastic rubber composition. In order to know the fluidity of the obtained thermoplastic rubber composition, using a melt indexer manufactured by Toyo Seiki Seisaku-Sho, Ltd., according to JIS K7210, a load of 21.6 kg, MFR which is an index of fluidity at a temperature of 190 ° C. ( (Melt flow rate) was measured. In addition, in order to know the gel content in the thermoplastic rubber composition, in accordance with JIS K 6388, measurement of unextracted residues in benzene was performed using a Harris basket made of a 100-mesh stainless steel wire mesh, and the gel content was calculated by the following equation. .

GL = L1−L2 where GL: gel content (% by weight) L1: residue not extracted into benzene of thermoplastic rubber composition (% by weight) L2: thermoplastic resin not extracted into benzene of elastic composition (% by weight) Table 1 shows the measured MFR and gel content.

Example 2 followed Example 1 except that the polyethylene of Example 1 was changed to polypropylene.

Example-1 was prepared in the same manner as in Example-1 except that the chlorosulfonated polyethylene of Example-1 was changed to chlorinated polyethylene.
Followed.

Example-1 was performed in the same manner as in Example-1, except that EPOCOAT 828 manufactured by Yuka Shell Epoxy Co., Ltd., which is an epoxy compound of Example-1, was changed to Epototo YD-128G manufactured by Toto Kasei Co., Ltd., which is an epoxy compound. Followed.

Comparative Example-1 followed Example-1 except that addition and kneading were not performed except for Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. which is the epoxy compound of Example-1.

Comparative Example-2 followed Example-1, except that 1,3,5-trithiocyanuric acid of Example-1 was changed to N, N'-m-phenylenebismaleimide.

Comparative Example-3 was prepared in the same manner as in Example-1 except that 1,3,5-trithiocyanuric acid in Example-1 was changed to diphenylguanidine.
Followed.

In Comparative Example-4, 1,3,5-trithiocyanuric acid of Example-1 was changed to diphenylguanidine, and no kneading was performed except for an epoxy compound, Epicoat 828 manufactured by Yuka Shell Epoxy Co., Ltd. Other than that, Example 1 was followed.

As can be seen from Table 1, the MFRs of Examples-1 to 4 show extremely large values as compared with Comparative Examples-1 to 4, indicating that the fluidity in the molding process is excellent.

(Effect of the Invention) As is clear from the above description, the gel content of the present invention
The thermoplastic rubber composition comprising chlorinated polyethylene and / or chlorosulfonated polyethylene containing not less than 10% by weight, a thermoplastic resin, a dehydrochlorination scavenger, a mercaptotriazine-based compound, and an epoxy-based compound solves flow characteristics in molding processing. It can be seen that the obtained thermoplastic rubber composition is used.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 23/26-23/36

Claims (1)

(57) [Claims] 1. A chlorinated polyethylene and / or chlorosulfonated polyethylene 10 containing a gel content of 20% by weight or more.
0 parts by weight per thermoplastic resin (excluding polyvinyl chloride)
A thermoplastic rubber composition containing 5 to 50 parts by weight, 0.1 to 30 parts by weight of a dehydrochlorination scavenger, 0.1 to 10 parts by weight of a mercaptotriazine compound, and 0.1 to 20 parts by weight of an epoxy compound.