JP3013501B2 - Chlorine-containing rubber crosslinked composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorine-containing rubber crosslinked composition. More specifically, the present invention provides a novel crosslinked composition for crosslinking chlorinated polyethylene and / or chlorosulfonated polyethylene.

[0002]

2. Description of the Related Art Conventionally, chlorinated polyethylene and / or chlorosulfonated polyethylene have been crosslinked and used as rubber products. As the crosslinking method, in the case of chlorinated polyethylene which is a chlorine-containing rubber, crosslinking with thioureas, crosslinking with amines / amine salts, crosslinking with organic peroxides, crosslinking with thiol derivatives, crosslinking with sulfur derivatives. Crosslinking with silanes and electron beams are known (Polymer Digest 1988, October 23, November, p. 33). Practically used in these crosslinking methods are crosslinking with organic peroxides and crosslinking with thiol derivatives (Japanese Patent Publication Nos. 54-15458 and 55-3).
9250 and JP-A-58-222129), the crosslinking of chlorinated polyethylene rubber is extremely limited. Further, the crosslinking of chlorosulfonated polyethylene, which is a chlorine-containing rubber, is also extremely limited. For this reason, there is a strong demand for a novel crosslinked composition that can crosslink chlorinated polyethylene and / or chlorosulfonated polyethylene and that can be put to practical use.

[0003]

SUMMARY OF THE INVENTION As a result of intensive studies, the present inventors have provided a novel cross-linked composition capable of cross-linking a chlorine-containing rubber and providing a cross-linked chlorine-containing rubber composition which can be put to practical use. It is.

[0004]

SUMMARY OF THE INVENTION The present invention is a novel crosslinked composition capable of crosslinking a chlorine-containing rubber comprising chlorinated polyethylene and / or chlorosulfonated polyethylene, phenolic resin, and a metal salt of an organic acid. . 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 chlorine gas is blown in 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.

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. A chlorosulfonyl group is introduced by an addition reaction, 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 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 phenolic resin used in the present invention refers to the addition / condensation of phenols such as phenol, cresol and xylenol with aldehydes such as formaldehyde, paraformaldehyde and furfural. It is a resin made by the reaction. Depending on the manufacturing method, there are novolak type and resole type (Murahashi, Oda, Imoto; Plastic Handbook, p. 129, Asakura Shoten, 196)
9). In the present invention, a novolak type and / or a resol type can be used. Examples of commercially available phenolic resins include, for example, data on chemicals from inside and outside Japan.
There is a phenol resin published in M. Co. (1990). These may be used alone or as a mixture. 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 and / or chlorosulfonated polyethylene. If the amount is less than 1 part by weight, the amount of crosslinking by the phenol resin is small, resulting in poor mechanical properties. If the amount exceeds 30 parts by weight, the rubber elasticity is undesirably lost due to the effect of the phenol resin.

The metal salt of an organic acid according to the present invention is a metal salt of a carboxylic acid type organic acid. The carboxylic acid type organic acid constituting the metal salt of an organic acid has a saturated carbon number of 6 or more. There are fatty acids and unsaturated fatty acids, chain organic acids having less than 6 carbon atoms, aromatic organic acids, and cyclic organic acids.

As a saturated fatty acid having 6 or more carbon atoms, for example,
Caproic acid, enanthic acid, caprylic acid, pelargonic acid,
As unsaturated fatty acids having 6 or more carbon atoms, such as capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, pargaric acid, stearic acid, arachiic acid, behenic acid, lignoceric acid, serotinic acid, montanic acid, and melicic acid, , Hexenoic acid, heptenoic acid, octenoic acid, nonenic acid, decylenic acid, undecylenic acid, dodecylenic acid,
Palmitoleic acid, oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid, linoleic acid, linoleic acid,
Monobasic fatty acids such as eleostearic acid, ricanoic acid, parinaric acid, tarilic acid, cadrainic acid, arachidonic acid, setreic acid, erucic acid, and selacoleic acid, and dibasic and tribasic acid fatty acids No.

As a chain organic acid having less than 6 carbon atoms, for example,
Formic acid, acetic acid, propionic acid, butyric acid, valeric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, trimethylacetic acid, vinylacetic acid, crotonic acid, fumaric acid, maleic acid, glycolic acid, lactic acid, methoxyacetic acid And monobasic acid type linear organic acids such as acrylic acid, and dibasic and tribasic acid type fatty acids.

Examples of the aromatic organic acid include benzoic acid, phenylacetic acid, hydrocinnamic acid, phenylbutyric acid, phenylvaleric acid, phenylcaproic acid, phenylenanoic acid, phenylcaprylic acid, phenylperargonic acid, phenylcapric acid, and benzoyl. Acrylic acid, phenylcyclohexylic acid, phenylbenzoic acid, phenylundecanoic acid, naphthoic acid, phthalic acid, meharritic acid, toluic acid, salicylic acid, acetylsalicylic acid, and the like, as a cyclic organic acid, for example, cyclopropanecarboxylic acid, Cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, cycloheptanecarboxylic acid, heptylcyclopentylacetic acid, octylcyclopentylacetic acid, nonylcyclopentylacetic acid, undecylcyclopentylacetic acid, pentylcyclo Hexyl acetate, heptyl cyclohexyl acetate, nonyl cyclohexyl acetate, undecyl cyclohexyl acetate, octyl cyclopentyl acid, undecyl cyclopentyl acid, penta cyclopentyl acid,
Hexacyclopentylbutyric acid, decylcyclohexylpropionic acid, dodecylcyclohexylpropionic acid, tetradecylcyclohexylpropionic acid, cyclohexylpropionic acid, cyclohexylbutyric acid, cyclohexylcaproic acid, cyclohexylcapric acid, cyclohexyllauric acid, naphthenic acid, camphoranoic acid, maleprolic acid Aromatic organic acids and cyclic organic acids such as maleprestinic acid, hydnocarpic acid, methylene octadecenoic acid, dimer acid, and resin acid are included.

The metals constituting the metal salt of an organic acid include, among the 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. , V
Vanadium, chromium, manganese, VIII
Group IV iron, cobalt, nickel, 5th period IV group b subgroup tin, 6th period IV group b subgroup lead.

The metal salt of an organic acid referred to in the present invention refers to a compound composed of the organic acid and the metal. The metal salt of this organic acid is used alone or as a mixture. The metal salts of these organic acids exhibit an effect when used in combination with the above-mentioned phenol resin. The amount used is 0.1 to 20 parts by weight, preferably 1 to 15 parts by weight, more preferably 2 to 10 parts by weight per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene. If the amount is less than 0.1 part by weight, the amount of crosslinking is small and the mechanical properties are inferior. If the amount exceeds 20 parts by weight, the amount of crosslinking increases, and the rubber elasticity is undesirably lost. The method for producing the crosslinked composition of the present invention is not particularly limited. For example, the composition is kneaded and compounded by a kneading machine such as a kneading roll machine, an internal mixer, and a double-armed kneader. The crosslinking temperature is 100 ° C. or higher, which is the usual crosslinking temperature of rubber.

[0014]

The invention is illustrated by the following examples.
The present invention is not limited to only these examples.

Chlorinated polyethylene as a chlorine-containing rubber used in Examples, Comparative Examples and Reference Examples was produced by the following method. In a 30 liter reactor, 17.5 carbon tetrachloride was added.
In accordance with the Ritzer and JIS K-6760, a temperature of 190
2.8 kg of high-density polyethylene having a melt index of 5.2 measured at a temperature of 2160 g and a load of 2160 g was added thereto, and the temperature was raised to 100 ° C. with stirring to dissolve the high-density polyethylene in carbon tetrachloride. Next, chlorine gas was blown in from the lower part of the reactor at a rate of 2.8 liters / min.
To obtain a solution of chlorinated polyethylene in carbon tetrachloride. Carbon tetrachloride was removed from this solution by a drum dryer to obtain solid chlorinated polyethylene.

Examples 1 to 5, Comparative Examples 1 to 4 and Reference Examples 1 and 2 Table 1 shows the formulations used in the Examples, Comparative Examples and Reference Examples. First, using an 8-inch roll manufactured by Toyo Seiki Seisaku-Sho, Ltd., the compounds of Examples, Comparative Examples and Comparative Examples were kneaded, and the kneaded material was compressed using a compression molding machine having a mold temperature of 180 ° C. Crosslinking was performed for 20 minutes to obtain a crosslinked rubber sheet having a thickness of 2 mm. Next, JIS K using the obtained rubber sheet
Hardness test, tensile test according to 6301, 72 at 120 ° C
Change rate by air heating aging test and NO. Using 3 oils, the volume change was measured by an immersion test at 120 ° C. for 72 hours. Table 1 shows the test results.

From Table 1, the examples have higher tensile strength and a lower rate of change by the air heating aging test than the comparative examples.
Further, since the volume change by the immersion test is small, it can be seen that the cross-linking is sufficient. Further, the examples show trithiocyanoic acid, which is the thiol derivative of Reference Example 1, and Reference Example-2.
The results are comparable to those of the crosslinked rubber sheet obtained by crosslinking with dicumyl peroxide.

[0018]

[Table 1]

[0019]

As is apparent from the above description, the chlorine-containing rubber crosslinked composition comprising the chlorinated polyethylene and / or chlorosulfonated polyethylene of the present invention, a phenolic resin and a metal salt of an organic acid is chlorinated. Polyethylene and / or
Alternatively, it is a novel composition for crosslinking chlorosulfonated polyethylene, and can be sufficiently provided for practical use.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ identification code FI C08L 61:06) (C08L 23/34 61:06) (58) Investigated field (Int.Cl. ⁷ , DB name) C08L 23 / 28 C08L 23/34 C08L 61/06 C08J 3/24 C08K 5/098 WPI (DIALOG)

Claims (1)

(57) [Claims] 1. A chlorine-containing rubber crosslinked composition comprising 1 to 30 parts by weight of a phenol resin and 0.1 to 20 parts by weight of a metal salt of an organic acid per 100 parts by weight of chlorinated polyethylene and / or chlorosulfonated polyethylene. object.