JP2838313B2 - Chlorinated polyethylene composition - Google Patents

Description

The present invention relates to a chlorinated polyethylene composition. More specifically, the present invention relates to an excellent chlorinated polyethylene composition having strong strength.

[Prior Art] As for chlorinated polyethylene, an aqueous suspension method and a solution method using an organic solvent are known from the difference in the production method.

Chlorinated polyethylene with a chlorine content of 5 to 45% by weight is fully crosslinked to provide excellent mechanical specialty, heat resistance,
It is a rubber material having weather resistance, ozone resistance, chemical resistance, and oil resistance, and is used in various industrial fields.

Organic peroxides are mainly used as a crosslinking method for chlorinated polyethylene, and other crosslinking methods using thiourea derivatives and thiuram sulfides have been proposed.In recent years, many studies using mercaptotriazines as crosslinking agents have been reported. Have been.

However, vulcanization of chlorinated polyethylene with organic peroxides does not have a specific cross-linking point, so the cross-linking reaction does not proceed easily, and produces a gas with a strong pungent odor during vulcanization, resulting in product Even the odor remains. In the presence of air, there is a problem that vulcanization is delayed due to vulcanization, and the vulcanized product is liable to foam. Further, since the vulcanized product is dangerous, storage and handling of the product require attention.

On the other hand, the crosslinking method using a thiourea derivative or thiuram sulfide has a delay in vulcanization and requires a long vulcanization time.

Further, mercaptotriazines as a crosslinking agent, di-n-butylamine, mono-n-butylamine as an accelerator,
In the crosslinking method using dicyclohexylamine or the like, there is a problem that an unpleasant odor is generated during the vulcanization operation and the odor remains in the product. There are also problems such as scorch.

[Problems to be Solved by the Invention] An object of the present invention is to provide a novel vulcanization system of chlorinated polyethylene.

In particular, it is to provide a novel vulcanization system using mercaptotriazines and quaternary ammonium salts. In addition, it is an object of the present invention to provide a novel vulcanization system which does not generate an unpleasant odor during vulcanization, has no odor in the product, does not easily scorch, and has no vulcanization delay.

[Means for Solving the Problems] The inventors of the present invention have conducted intensive studies based on the above-mentioned technical recognition, and as a result, in a crosslinking method using mercaptotriazines, a more specific quaternary ammonium salt was added to mercaptotriazines. The present inventors have found that the crosslinking reaction can be rapidly advanced by the addition and use thereof, and the present invention has been accomplished.

That is, the present invention relates to 0.1 to 5 parts by weight of a mercaptotriazine represented by the following general formula [I] and 0.2 to 5 parts by weight of a quaternary ammonium salt represented by the following general formula [II] based on 100 parts by weight of chlorinated polyethylene. In a chlorinated polyethylene composition comprising 10 parts by weight and 1 to 30 parts by weight of an acid acceptor.

(Where R is a mercapto group, an alkyl group, an aryl group, a hydrogen group, an alkylamino group, a dialkylamino group,
Cycloalkylamino group, dicycloalkylamino group,
Arylamino group, alkoxyl group, N-alkyl-N
-Represents an arylamino group. R ₁ R ₂ R ₃ R ₄ NX [II] (where R _{1 to} R ₄ are an alkyl group, an aryl group, an allyl group, X is a halogen, and R _{1 to} R ₄ are different from each other even if R _{1 to} R ₄ are the same) Hereinafter, the present invention will be described in detail.

Specific examples of the mercaptotriazines represented by the general formula [I] constituting the crosslinking system of the present invention include 1,3,5-trithiocyanuric acid, 1-methoxy-3,5-dimercaptotriazine, -Hexylamino-3, -5-dimercaptotriazine, 1-diethylamino-3,5-dimercaptotriazine, 1-cyclohexylamino-3,5-dimercaptotriazine, 1-butylamino-3,5-dimercaptotriazine And 1-phenylamino-3,5-dimercaptotriazine.

The amount of addition is 0.1 to 5 parts by weight of mercaptotriazine per 100 parts by weight of chlorinated polyethylene. If the amount is less than 0.1 part by weight, the strength of the obtained vulcanizate is weak, and if it exceeds 5 parts by weight, the effect does not change. Most preferably, it is 0.3 to 3 parts by weight.

Specific examples of the quaternary ammonium salts represented by the general formula [II] in the present invention include stearyltrimethylammonium bromide, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, phenyltrimethyl bromide Ammonium, phenyltrimethylammonium chloride, phenyltrimethylammonium iodide, allyltriethylammonium bromide and the like.

The addition amount is 4 parts per 100 parts by weight of chlorinated polyethylene.
0.2 to 10 parts by weight of quaternary ammonium salts. If the amount is less than 0.2 part by weight, the vulcanization rate becomes slow, and if the amount exceeds 10 parts by weight, the effect does not change, but there is a risk of scorch, which is not preferable. Most preferably, it is 0.3 to 6 parts by weight.

The chlorinated polyethylene referred to in the present invention has a chlorine content of 5 to 45% by weight and is produced by a suspension method and a solution method.

In the suspension method, the raw material polyethylene powder is reacted with chlorine in a water slurry. The resulting chlorinated polyethylene has a non-uniform chlorine distribution and a small amount of polyethylene, leaving a small amount of soap and other impurities.

On the other hand, in the solution method, the raw material polyethylene is dissolved in a solvent to react chlorine. The resulting chlorinated polyethylene has a uniform distribution of chlorine and no impurities.

The present invention is applicable to chlorinated polyethylene produced by any production method.

In addition, the chlorinated polyethylene referred to in the present invention is a chlorinated ethylene-based copolymer, a chlorinated ethylene / butene-1 copolymer, a chlorinated ethylene / propylene copolymer,
The term includes chlorinated ethylene / α-olefin copolymers such as chlorinated ethylene / hexene-1 copolymer.

Although the composition of the present invention using the chlorinated polyethylene obtained by the suspension method has a tendency to slightly shorten the scorch time, it does not generate an unpleasant odor during the vulcanization operation, and the product has no odor and has a strong odor. A sulphate is obtained.

On the other hand, the composition of the present invention using the chlorinated polyethylene obtained by the solution method shows a good scorch time, does not generate an unpleasant odor during the vulcanization work, has no odor of the product, and is resistant to the vulcanized molded product. A strong vulcanizate excellent in compression set test can be obtained. For this reason, it is preferable to use chlorinated polyethylene obtained by a solution method.

In the compositions of the present invention, fillers, reinforcing agents, plasticizers, antioxidants, processing aids commonly employed in the art,
Pigments and the like can be freely blended as appropriate.

It is necessary to mix a certain metal oxide which can serve as an acid acceptor in the composition of the present invention from the viewpoint of thermal stability of the vulcanized product.

The addition amount is 1 to 30 parts by weight of the metal oxide based on 100 parts by weight of the chlorinated polyethylene. If it is less than 1 part by weight, the acid receiving effect is small, and if it exceeds 30 parts by weight, the acid receiving effect remains unchanged.
Rather, the vulcanized product is hard, which is not preferable. Most preferably, it is 2 to 20 parts by weight.

Examples of the metal oxide include oxides, hydroxides, silicates, carboxylates, carbonates, borates and phosphites of metals belonging to Group II of the periodic table, and specific examples include magnesium oxide. , Calcium oxide, magnesium hydroxide, calcium hydroxide, magnesium carbonate, calcium carbonate, calcium silicate, calcium stearate, calcium phthalate, calcium phosphite and the like. In addition, an oxide of a Group IVa metal of the periodic table, a basic carbonate, a basic carboxylate, a basic phosphite, a basic sulfite, and a tribasic sulfate are specific examples of litharge, Examples include lead red, tin oxide, zinc oxide, dibasic lead phthalate, dibasic lead carbonate, basic lead phosphite, basic lead sulfite, and tribasic lead sulfate.

As a method of mixing various compounds with the chlorinated polyethylene, an open roll, a Banbury, a kneader, or the like can be used.

For the production of a crosslinked product of the composition of the present invention, various means conventionally performed in the technical field, such as press vulcanization,
Steam vulcanization, hot air vulcanization, etc. can be used.

The composition of the present invention is suitable for molded products such as electric wires, oil-resistant and solvent-resistant hoses, gaskets, packings, diaphragms, automobile boots and belts.

[Effect of the Invention] In the vulcanization system of mercaptotriazines of chlorinated polyethylene according to the present invention, the crosslinking reaction proceeds promptly,
It is possible to obtain a vulcanized product which does not generate an unpleasant odor during the vulcanization operation, has no odor in the product and has sufficient strength.

[Examples] Next, the present invention will be described in more detail based on examples, but these are examples for assisting the present invention, and the present invention is not limited at all by these examples.

The suspension chlorinated polyethylene used in the following examples is a commercial product, Eraslen, trade name of Showa Denko KK
301A was used.

On the other hand, solution-method chlorinated polyethylene is prepared by dissolving polyethylene in a
Chlorinated polyethylene having a chlorine content of 30% by weight synthesized by blowing chlorine gas at a temperature of 2.5 ° C. and a reaction pressure of 2.5 kg / cm ² was used.

Example 1 A solution-processed chlorinated polyethylene, magnesium oxide, FEF carbon, and a plasticizer DOS were kneaded with a Banbury mixer in the proportions and proportions shown in Table 1 (part 1), and then the crosslinking agents 1, 3, and 5 were mixed.
-Trithiocyanuric acid and accelerator stearyltrimethylammonium bromide were added with an 8-inch oprol to obtain a chlorinated polyethylene composition.

The unvulcanized product of this composition was prepared using a Mooney scorch meter (manufactured by Shimadzu Corporation) at a scorch time (t
5: min) was measured.

The vulcanization characteristics were measured using a monsanto rheometer at a temperature of 160 ° C and a swing angle of 3 ° (LB-I
N) was measured.

On the other hand, the above composition was pressed at a temperature of 160 using a press vulcanizer.
The mixture was heated in a mold at 120 ° C. and a pressure of 120 km / cm ² for 30 minutes to obtain a vulcanized molded product. The properties of the obtained vulcanized molded product were measured by a tensile test and a compression set test (test conditions: 120 ° C. × 22 hours).

 The measuring method was obtained in accordance with JIS K6301.

During the vulcanization of the above composition, the state of generation of unpleasant odor and the odor of the vulcanized molded product were carefully observed. The results are shown in Table 1 (Part 2).

Example 2 Example 1 was repeated except that the chlorinated polyethylene composition was obtained by changing the solution-method chlorinated polyethylene of Example 1 to the suspension-method chlorinated polyethylene in the proportions and proportions shown in Table 1 (Part 1). The same was done.

 The results are shown in Table 1 (Part 2).

Example 3 A chlorinated polyethylene composition was obtained by changing the stearyltrimethylammonium bromide of Example 1 to tetra-n-butylammonium iodide in the proportions and proportions shown in Table 1 (part 1). Performed similarly to 1.

 The results are shown in Table 1 (Part 2).

Example 4 The solution method chlorinated polyethylene of Example 1 was changed to the suspension method chlorinated polyethylene in the proportions and proportions shown in Table 1 (part 1), and stearyltrimethylammonium bromide was changed to tetra-n-butylammonium iodide. The procedure was performed in the same manner as in Example 1 except that a chlorinated polyethylene composition was obtained.

 The results are shown in Table 1 (Part 2).

Example 5 The composition and ratio shown in Table 1 (Part 1)
1,3,5-trithiocyanuric acid is converted to 1-phenylamino-
A chlorinated polyethylene composition was obtained in the same manner as in Example 1, except that 3,5-dimercaptotriazine was used, and stearyltrimethylammonium bromide was used instead of tetra-n-butylammonium iodide.

 The results are shown in Table 1 (Part 2).

Example 6 The composition and ratio shown in Table 1 (Part 1)
1,3,5-trithiocyanuric acid is converted to 1-butylamino-3,5
-Same as Example 1 except that dimercaptotriazine was used and stearyltrimethylammonium bromide was used instead of tetra-n-butylammonium iodide to obtain a chlorinated polyethylene composition.

 The results are shown in Table 1 (Part 2).

As shown in Table 1 (Part 2), the observation and measurement results of Examples 1 to 6, the solution method chlorinated polyethylene composition,
Although the scorch time of the suspension method chlorinated polyethylene composition is slightly shorter, the suspension method chlorinated polyethylene composition does not generate an unpleasant odor during the vulcanization work in any of the examples, and the vulcanized molded product has an odor. And exhibited an excellent compression set test.

Comparative Example 1 The chlorinated polyethylene composition was prepared by changing the solution-method chlorinated polyethylene of Example 1 to the suspension-method chlorinated polyethylene and changing stearyltrimethylammonium bromide to dicyclohexylamine in the proportions and proportions shown in Table 2 (Part 1). Except having obtained the thing, it carried out similarly to Example 1.

 The results are shown in Table 2 (part 2).

As a result of observation and measurement, an unpleasant odor was generated during the vulcanization operation, and the odor remained in the vulcanized molded product.

Comparative Example 2 The chlorinated polyethylene composition was obtained by changing the solution-method chlorinated polyethylene of Example 1 to the suspension-method chlorinated polyethylene in the proportions and proportions shown in Table 2 (part 1), and excluding stearyltrimethylammonium bromide. The procedure was performed in the same manner as in Example 1 except for the above.

 The results are shown in Table 2 (part 2).

With this composition, the torque of the rheometer did not increase, and a vulcanized molded product could not be obtained.

Comparative Example 3 The chlorinated polyethylene of the solution method of Example 1 was changed to the chlorinated polyethylene of the suspension method, and the stearyltrimethylammonium bromide was changed to di-n-butylamine in the proportions and proportions shown in Table 2 (Part 1). Except having obtained the chlorinated polyethylene composition, it carried out similarly to Example 1.

 The results are shown in Table 2 (part 2).

As a result of observation and measurement, an unpleasant odor was generated during the vulcanization operation, the odor remained on the vulcanized molded product, and the compression set test was inferior.

Comparative Example 4 The chlorinated polyethylene of the solution method of Example 1 was changed to the chlorinated polyethylene of the suspension method in the proportions and proportions shown in Table 2 (Part 1), and 1,3,5-trithiocyanuric acid was replaced with 1-phenyl. A chlorinated polyethylene composition was obtained in the same manner as in Example 1, except that amino-3,5-dimercaptotriazine was used and stearyltrimethylammonium bromide was used instead of dicyclohexylamine.

 The results are shown in Table 2 (part 2).

As a result of observation and measurement, an unpleasant odor was generated during the vulcanization operation, the odor remained on the vulcanized molded product, and the compression set test was inferior.

Comparative Example 5 The solution chlorinated polyethylene of Example 1 was changed to the suspension chlorinated polyethylene in the proportions and proportions shown in Table 2 (part 1), and 1,3,5-trithiocyanuric acid was replaced with 1-butyl. A chlorinated polyethylene composition was obtained in the same manner as in Example 1, except that amino-3,5-dimercaptotriazine was used and stearyltrimethylammonium bromide was used instead of dicyclohexylamine.

 The results are shown in Table 2 (part 2).

As a result of observation and measurement, an unpleasant odor was generated during the vulcanization operation, the odor remained in the vulcanized molded product, the scorch time was slightly short, and the compression set test was poor.

As is clear from the above Examples and Comparative Examples, the chlorinated polyethylene composition obtained by the present invention does not generate an unpleasant odor during the vulcanization operation, and has a strong strength with no odor in the product. It is an excellent composition to have.

Claims (1)

(57) [Claims] 1. A mercaptotriazine represented by the following general formula [I]: 0.1 to 100 parts by weight of chlorinated polyethylene.
A chlorinated polyethylene composition comprising about 5 parts by weight, 0.2 to 10 parts by weight of a quaternary ammonium salt represented by the following general formula [II], and 1 to 30 parts by weight of an acid acceptor. (Where R is a mercapto group, an alkyl group, an aryl group,
A hydrogen group, an alkylamino group, a dialkylamino group, a cycloalkylamino group, a dicycloalkylamino group, an arylamino group, an alkoxyl group, and an N-alkyl-N-arylamino group. ) R ₁ R ₂ R ₃ R ₄ NX [II] (where R _{1 to} R ₄ are an alkyl group, an aryl group, an allyl group,
X represents a halogen. )