JP3158558B2 - Method for producing thermoplastic elastomer composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a thermoplastic elastomer composition, and more particularly to a method for producing a novel thermoplastic elastomer composition having improved flowability during molding. The method for producing the thermoplastic elastomer composition of the present invention is used in the field of resin processing and rubber processing.

[0002]

2. Description of the Related Art Conventionally, a thermoplastic elastomer comprising a rubber containing a gel component and a thermoplastic resin obtained by vulcanizing the rubber by dynamic heat treatment while kneading the rubber and the thermoplastic resin.
Since it has thermoplasticity and rubber elasticity, it is molded at high temperature using the thermoplasticity of thermoplastic elastomer,
Used within a temperature range having rubber elasticity. Generally, thermoplastic elastomers have the advantages that they flow easily at high temperatures, are easy to mold, and have a short molding time. In addition, the vulcanization process is required for rubber molding, but thermoplastic elastomer is required.
In the case of rubber, it is not necessary, for example, because it is superior to rubber in terms of energy consumption or labor cost,
It has come to be widely used in the resin and rubber fields.

In recent years, chlorinated polyethylene or chlorosulfonated polyethylene has better physical properties such as oil resistance, ozone resistance, weather resistance and lightness than other rubbers. The fluorinated polyethylene and the thermoplastic resin are kneaded and vulcanized by dynamic heat treatment to be used as a thermoplastic elastomer. However, in order to contain the gel component, chlorination obtained by dynamic heat treatment using a conventionally used vulcanization system of a dehydrochlorination scavenger and a vulcanizing agent for rubber and / or a vulcanization accelerator for rubber. Thermoplastic elastomers containing polyethylene or chlorosulfonated polyethylene and a thermoplastic resin as main components include:
In molding at a high temperature of 00 ° C. or more, the fluidity is extremely poor. Also, Japanese Patent Publication Nos. 53-22104 and 55
-39250 and JP-B-54-15458, etc., a vulcanization system using a dehydrochloride scavenger and a triazine-based compound, or JP-A-52-90546, JP-B-56-2
2470 and Japanese Patent Publication No. 64-4536, etc., have extremely poor fluidity of thermoplastic elastomers produced using a dehydrochlorination scavenger and a vulcanization system using a combination of a dimaleimide compound and an organic peroxide. . Therefore, the molding cycle is slow in molding with an injection molding machine, and a product with a complicated shape cannot be molded. In the extrusion molding with an extruder, the extrusion speed is slow, and a product with a complicated shape cannot be molded. There is. Further, a thermoplastic elastomer using an organic peroxide is disclosed in JP-A-52-29845, but chlorinated polyethylene or chlorosulfonated polyethylene contains chlorine in the molecule, and thus is made of an organic peroxide. Poor cross-linking efficiency, a large amount of organic peroxide is required to obtain the required amount of gel component, and when a thermoplastic resin other than polypropylene is used, the thermoplastic resin is gelled to form a thermoplastic elastomer. It has drawbacks such as not being obtained or poor fluidity.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have provided a method for producing a thermoplastic elastomer composition in which fluidity has been solved in molding processing. is there.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a chlorinated polyethylene or chlorosulfonated polyethylene, which comprises kneading a metal salt of an organic acid, an epoxy resin, a dehydrochloric acid scavenger and a thermoplastic resin, and performing a dynamic heat treatment. And a method of adding and kneading a dehydrochlorination scavenger. 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, Powders or particles of ethylene-methyl acrylate 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. is there. 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.

[0007] The chlorosulfonated polyethylene used in the present invention means that the polymer is dissolved in an inert organic solvent such as carbon tetrachloride, chlorine gas is blown into the chlorinated polymer, and then chlorosulfonyl is converted. Either a chlorosulfonyl group is introduced by an addition reaction, or chlorine and a chlorosulfonyl group are introduced with chlorosulfonyl to form a rubber. The amount of chlorine is not particularly limited as long as the chlorosulfonated polyethylene is rubbery like the chlorinated polyethylene, but 15 to 55% by weight of the chlorosulfonated polyethylene is in a rubbery state. The production methods of chlorinated polyethylene and chlorosulfonated polyethylene have been described above, but the chlorinated polyethylene or chlorosulfonated polyethylene used in the present invention is not limited to these production methods. The metal salt of an organic acid used in the production method of the present invention is a metal salt of a carboxylic acid-type organic acid, and the carboxylic acid-type organic acid constituting the metal salt of the organic acid has 6 carbon atoms. The above saturated fatty acids and unsaturated fatty acids, chain organic acids having less than 6 carbon atoms, aromatic organic acids, and cyclic organic acids are included.

As a saturated fatty acid having 6 or more carbon atoms, for example,
Unsaturated fatty acids having 6 or more carbon atoms, such as caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, stearic acid, behenic acid, cerotic acid, and melicic acid, for example, hexenoic acid, octenoic acid, decylene acid, dodecylenic acid , Oleic acid, petroselinic acid, vaccenic acid, lino-
Monobasic acid-type fatty acids such as luic acid, eleostearic acid, parinaric acid, tarilic acid, arachidonic acid, and erucic acid, and dibasic and tribasic acid-type fatty acids thereof. Examples of the chain organic acids having less than 6 carbon atoms include monobasic acids such as formic acid, propionic acid, valeric acid, malonic acid, glutaric acid, vinyl acetic acid, fumaric acid, maleic acid, glycolic acid, acrylic acid, etc. And their dibasic and tribasic acids. As aromatic organic acids, for example, benzoic acid, hydrocinnamic acid, phenylvaleric acid, phenylenanoic acid, phenylperargonic acid, benzoylacrylic acid, phenylbenzoic acid, phthalic acid, mecharitic acid, salicylic acid, acetylsalicylic acid, etc. As a cyclic organic acid, for example, cyclopropanecarboxylic acid, cyclopentanecarboxylic acid, cycloheptanecarboxylic acid, nonylcyclopentylacetic acid, pentylcyclohexylacetic acid, nonylcyclohexylacetic acid, undecylcyclohexylacetic acid, undecylcyclopentylbutyric acid, hexacyclopentylbutyric acid, dodecylcyclohexyl Aromatic organic acids and rings such as propionic acid, cyclohexylpropionic acid, cyclohexylcaproic acid, naphthenic acid, maleprolic acid, methylene octadecenoic acid, dimer acid, and resin acid Organic acids.

The metal constituting the metal salt of an organic acid includes, among metals of transition elements having a plurality of valences, copper of Group I and Group B of the fourth period of the periodic table, germanium of Group IV, and titanium of Group IV. ,
Vanadium, chromium, manganese of group V to VIIa,
Refers to Group VIII iron, cobalt, nickel, tin of the 5th period Group IV b-subgroup, and lead of the 6th period Group IV b-subgroup.

The term "metal salt of an organic acid" as used in the present invention means a compound composed of the above-mentioned organic acid and a metal. The metal salt of this organic acid is used alone or as a mixture. The amount used is 0.1 to 20 parts by weight per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene,
Preferably from 0.5 to 10 parts by weight, more preferably from 1 to 5 parts by weight.
Parts by weight are used. If the amount is less than 0.1 part by weight, the gel content due to the dynamic heat treatment is small and the mechanical properties are inferior. Even when used in an amount exceeding 20 parts by weight, no effect is exerted on the gel content, and the mechanical properties are poor due to the influence of the metal salt of the organic acid.

The epoxy resin used in the present invention is a compound prepared by reacting a compound having an active group such as a hydroxyl group, a carboxyl group or an amino group with epichlorohydrin and having two or more epoxy groups. Epoxy compounds prepared by the reaction of bisphenol A with epichlorohydrin, epoxidized novolak compounds prepared by the reaction of novolak and epichlorohydrin, epoxidized cresol compounds, epoxidized alcohol compounds, epoxidized methacrylic acid compounds, epoxy compounds Phenyldiamine compound and the like. Examples of commercially available epoxy resins include, for example, data on chemicals from home and abroad B Functional polymers: Published by CMC Corporation (1990)
There are epoxy resins listed on These can be used alone or in combination. This epoxy resin
When used in combination with the above-mentioned metal salt of an organic acid, it is effective in producing a gel component by dynamic heat treatment. The amount used is 1 to 30 parts by weight, preferably 5 to 15 parts by weight, per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene. If the amount is less than 1 part by weight, the amount of the gel by the dynamic heat treatment is small and the mechanical properties are inferior. If used in an amount exceeding 30 parts by weight, no effect is exerted on the gel content, and the thermoplastic elastomer obtained under the influence of the epoxy resin is inferior in rubber elasticity, which is not preferred.

The dehydrochloric acid scavenger of the present invention refers to metal oxides and metal hydroxides that scavenge hydrochloric acid generated from chlorinated polyethylene or chlorosulfonated polyethylene by dynamic heat treatment. For example, zinc oxide, aluminum oxide, cadmium oxide, calcium oxide as metal oxides,
Cobalt oxide, tin oxide, iron oxide, titanium oxide, copper oxide,
Sodium oxide, lead oxide, nickel oxide, barium oxide, magnesium oxide, manganese oxide, lithium oxide,
Beryllium oxide and the like can be mentioned. Zinc hydroxide, aluminum hydroxide, cadmium hydroxide as metal hydroxide,
Examples thereof include chromium hydroxide, potassium hydroxide, calcium hydroxide, cobalt hydroxide, tin hydroxide, iron hydroxide, copper hydroxide, sodium hydroxide, lead hydroxide, barium hydroxide, and magnesium hydroxide. These are used alone or in combination. The amount used is 0.1 to 10 parts by weight per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene before dynamic heat treatment and 0.1 after dynamic heat treatment.
-30 parts by weight are used.

[0013] The thermoplastic resin used in the production method of the present invention is a resin that melts at a high temperature of 100 ° C or more,
For example, polyethylene, ethylene vinyl acetate copolymer, polypropylene, polystyrene, polyamide, thermoplastic polyurethane, polyvinyl chloride, polycarbonate, phenoxy resin, polymethyl methacrylate, methyl methacrylate / styrene copolymer Examples include polymers, fluororesins, polyvinyl butyral, polyvinyl formal, polyvinylidene chloride, chlorinated polyether, styrene / acrylonitrile copolymer, acrylonitrile / butadiene / styrene copolymer, polyacetal, and the like. . These can be used alone or in combination. The amount used is 5 to 50 parts by weight of a thermoplastic resin per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene. If the amount is less than 5 parts by weight, the fluidity of the obtained thermoplastic elastomer composition during molding at high temperatures is poor. If it exceeds 50 parts by weight, it does not exhibit elasticity, which is not preferable.

Apparatuses used in the method for producing the thermoplastic elastomer composition of the present invention include kneaders generally used for kneading rubber or resin, such as a roll kneader, a Banbury mixer, and a double arm. Shaped kneaders, screw type kneaders, rotor type continuous kneaders and the like are used.

The dynamic heat treatment referred to in the present invention refers to a kneader or the like described above, wherein chlorinated polyethylene or chlorosulfonated polyethylene is fluidized in the kneader while kneading with an epoxy resin and a metal salt of an organic acid. Refers to making sulfur by gelation. As the gel content, it is preferable that 20% by weight or more of chlorinated polyethylene or chlorosulfonated polyethylene is vulcanized and gelled. If the amount is less than 20% by weight, the mechanical properties of the thermoplastic elastomer composition are inferior and are not preferred. The temperature of the dynamic heat treatment is preferably from 100 to 240C. Thermoplastic elastomer obtained below 100 ° C
The dispersion of the thermoplastic resin therein is insufficient and the mechanical properties are poor, which is not preferable. When the dynamic heat treatment is performed at a temperature exceeding 240 ° C., the obtained thermoplastic elastomer composition may have poor mechanical properties or may turn blackish brown. The time required for performing the dynamic heat treatment varies depending on the type and amount of the epoxy resin and the metal salt of the organic acid used, the type of the kneader, and the like, and is not limited.

According to the production method of the present invention, a metal salt of an organic acid, an epoxy resin, chlorinated polyethylene or chlorosulfonated polyethylene is added to chlorinated polyethylene or chlorosulfonated polyethylene in advance by using the above-mentioned kneader. A dynamic heat treatment is carried out by kneading 0.1 to 10 parts by weight of a dehydrochlorination scavenger per part and a thermoplastic resin. The feature of the production method of the present invention is that after performing the dynamic heat treatment, the chlorinated polyethylene or chlorosulfonated polyethylene 1
0.1 to 30 parts by weight of a dehydrochlorination scavenger is added and kneaded per 100 parts by weight. By adding and kneading the dehydrochlorination scavenger in this step, the thermoplastic elastomer composition exhibits extremely excellent fluidity. If it is less than 0.1 part by weight, the effect of improving the fluidity is small. When added in excess of 30 parts by weight, there is an effect of improving fluidity, but no remarkable improvement effect can be expected. If the dehydrochlorination scavenger is not added and kneaded in this step, the fluidity of the thermoplastic elastomer composition is not improved. The temperature of addition and kneading of the dehydrochlorination scavenger is the same as that of the dynamic heat treatment.
00-240 is preferred.

In the process of producing the thermoplastic elastomer composition of the present invention, or the obtained thermoplastic elastomer,
In the composition, a compounding agent for rubber or a compounding agent for resin, for example, a plasticizer, a softening agent, an antioxidant, an ultraviolet absorber, a reinforcing agent such as carbon black, a white filler, a foaming agent, a lubricant, an antistatic agent. , A colorant and the like can be kneaded as necessary.

[0018]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

The chlorinated polyethylene used in Examples and Comparative Examples was produced by the following method. In a 30 liter reactor, 17.5 liters of carbon tetrachloride and JIS K-6
According to 760, 2.8 kg of high-density polyethylene having a melt index of 5.2 measured at a temperature of 190 ° C. and a load of 2160 g was added, and the temperature was raised to 100 ° C. with stirring.
High density polyethylene was dissolved in carbon tetrachloride. Next, chlorine gas was blown from the lower part of the reactor at a rate of 2.8 liters / minute to obtain a carbon tetrachloride solution of chlorinated polyethylene having a chlorine content of 35% by weight. Carbon tetrachloride was removed from this solution by a drum dryer to obtain solid chlorinated polyethylene.

Examples 1 to 5 and Comparative Examples 1 to 4 In Example 1, in the formulation of Table 1, 5 parts by weight of Epicoat 828 (epoxy resin) per 100 parts by weight of chlorinated polyethylene, Parts by weight and 2 parts by weight of magnesium oxide are kneaded by a roll kneader at 50 ° C., and the rubber kneaded material is set to a chamber set temperature of 160 ° C.
In a Brabender-Plastic-Doller-Roller-Mixer type, 15 parts by weight of polypropylene is melt-dispersed by utilizing the heat generated by the rubber kneaded material, and then 2 parts by weight of cobalt naphthenate is added to perform a dynamic heat treatment. After that, 8 parts by weight of magnesium oxide and 1 part by weight of Nocrack NS-6 were added and kneaded to obtain a thermoplastic elastomer composition.

To determine the gel content of the chlorinated polyethylene produced by the dynamic heat treatment in the thermoplastic elastomer composition, the gel content was measured according to the following method.

0.5 g of the thermoplastic elastomer composition was placed in 100 g of benzene, left at 23 ° C. for 24 hours, then stirred for 1 hour in a ball mill, and left for 1 hour to make the thermoplastic elastomer insoluble. The portion was settled, 5 g of the portion dissolved in benzene was taken out, and the benzene was evaporated, and its weight was measured. The gel content of the produced chlorinated polyethylene was calculated by the following equation.

GL = {[0.5− (L + P)] / 0.5} × 100, where GL: gel content (% by weight) L: thermoplastic elastomer dissolved in 100 g of benzene
Weight of composition P: indicates the weight of polypropylene in sample 0.5.

Next, in order to know the fluidity of the obtained thermoplastic elastomer composition, a melt indexer manufactured by Toyo Seiki Seisaku-sho, Ltd. was used at a load of 21.6 kg and a temperature of 190 ° C. according to JIS K7210. M as an indicator of liquidity
The measurement of FR (melt flow rate) was performed.

In order to know the mechanical properties of the obtained thermoplastic elastomer composition, a preheater was used in a compression molding machine at 180 ° C.
After performing pressure molding for 2 minutes, cooling was performed for 4 minutes with a 10 ° C. compression cooler to obtain a sheet having a thickness of 2 mm.
A tensile test was performed from the obtained sheet according to JIS K6301.

Table 1 shows the measured gel content, MFR and tensile test results.

Example 2 followed Example 1 except that 2 parts by weight of cobalt naphthenate of Example 1 was changed to 1 part by weight of iron naphthenate.

The third embodiment is different from the first embodiment in terms of the epicort 828.
(Epoxy resin) 5 parts by weight to 10 parts by weight, cobalt naphthenate 2 parts by weight to naphthenate 2 parts by weight, magnesium oxide 2 parts by weight to calcium hydroxide 4 parts by weight, polypropylene to polyethylene and magnesium oxide 8 Example 1 was repeated except that the weight part was changed to 16 parts by weight of calcium hydroxide.

In Example 4, the chlorinated polyethylene of Example 1 was replaced with chlorosulfonated polyethylene, and Epicoat 8
28 (epoxy resin) 5 parts by weight of Epototo YD-12
Example 1 was followed except that 10 parts by weight of 8G (epoxy resin) and 2 parts by weight of cobalt naphthenate were changed to 3 parts by weight of lead oleate.

In Example 5, the chlorinated polyethylene of Example 1 was replaced with chlorosulfonated polyethylene, and Epicoat 8
28 (epoxy resin) 5 parts by weight of Epototo YD-12
Example 1 was followed except that 10 parts by weight of 8G (epoxy resin) and 2 parts by weight of cobalt naphthenate were changed to 1 part by weight of iron naphthenate.

In Comparative Example 1, a thermoplastic elastomer composition was obtained by changing 8 parts by weight of magnesium oxide to 10 parts by weight of magnesium oxide except for 2 parts by weight of magnesium oxide of Example 1. The elastomer composition was powdery and the following tests were discontinued, including determination of gel content.

Comparative Example 2 followed Example 1 except that 8 parts by weight of magnesium oxide of Example 1 was omitted.

In Comparative Example 3, the chlorinated polyethylene of Example 1 was replaced with chlorosulfonated polyethylene, and Epicoat 8
28 (epoxy resin) 5 parts by weight of Epototo YD-12
8G (epoxy resin), 10 parts by weight of cobalt naphthenate, 1 part by weight of iron naphthenate, 2 parts by weight of magnesium oxide, and 8 parts by weight of magnesium oxide, 10 parts by weight of thermoplastic elastomer The composition was obtained, but the thermoplastic elastomer composition obtained was powdery and the following tests were stopped, including the measurement of the gel content.

In Comparative Example 4, the chlorinated polyethylene of Example 1 was replaced with chlorosulfonated polyethylene, and Epicoat 8
28 (epoxy resin) 5 parts by weight of Epototo YD-12
Example 1 was followed except that 10 parts by weight of 8G (epoxy resin), 2 parts by weight of cobalt naphthenate were changed to 3 parts by weight of lead oleate, and polypropylene was changed to polyethylene, and 8 parts by weight of magnesium oxide was removed. Table 1 shows the results.

The thermoplastic elastomer compositions of Examples 1 to 5 obtained by the method for producing the thermoplastic elastomer composition of the present invention showed excellent fluidity as compared with Comparative Examples 2 and 4. On the other hand, Comparative Examples 1 and 2 are thermoplastic elastomers.
The compositions became powdery, and Comparative Examples 2 and 4 exhibited mechanical properties similar to those of the Examples, but were extremely poor in fluidity.

[0036]

The metal salt of an organic acid, an epoxy resin, a dehydrochloric acid scavenger and a thermoplastic resin are kneaded with chlorinated polyethylene or chlorosulfonated polyethylene, and a dynamic heat treatment is performed. It can be seen that the production method characterized in that it is a method for producing a thermoplastic elastomer composition whose flowability has been solved in molding processing.

[Table 1]

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Claims (1)

(57) [Claims] 1. A metal salt of an organic acid is 0.1 per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene.
-20 parts by weight, 1-30 parts by weight of an epoxy resin, 0.1-10 parts by weight of a dehydrochloric acid scavenger and 5-50 parts by weight of a thermoplastic resin, and then a dynamic heat treatment is performed, and then chlorinated polyethylene or A process for producing a thermoplastic elastomer composition, comprising adding and kneading 0.1 to 30 parts by weight of a dehydrochlorinated scavenger per 100 parts by weight of chlorosulfonated polyethylene.