JP3019477B2 - 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 crosslinking with electron beams are known (Polymer Digest 1988, October 23, p. 23 and November 33).
page). Among these crosslinking methods, crosslinking with organic peroxides and crosslinking with thiol derivatives (JP-B-54-15458 and JP-B-55-392) are practically used.
50 and JP-A-58-222129), the crosslinking of chlorinated polyethylene 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 practically usable chlorine-containing rubber cross-linked composition. It is.

[0004]

SUMMARY OF THE INVENTION The present invention is a novel crosslinked composition capable of crosslinking chlorine-containing rubbers comprising chlorosulfonated polyethylene and / or chlorinated polyethylene, epoxy resins, and metal salts of organic acids.

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 make 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 and / or chlorosulfonated polyethylene used in the present invention is not limited to these production methods.

The epoxy resin used in the present invention is a resin produced by reacting a compound having an active group such as a hydroxyl group, a carboxyl group or an amino group with epichlorohydrin. The epoxy resin is formed by reacting bisphenol A with epichlorohydrin. Epoxy compounds made by the reaction,
Epoxidized novolak compound produced by the reaction of novolak with epichlorohydrin, epoxidized crezo-
Epoxidized alcohol compounds, epoxidized methacrylic acid compounds, epoxidized phenyldiamine compounds, and the like. For example, as a commercially available epoxy resin,
Domestic and foreign chemicals data B Functional polymer: There is an epoxy resin published in CMC Corporation (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, is used 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 epoxy resin is small, resulting in poor mechanical properties. If the amount exceeds 30 parts by weight, rubber elasticity is undesirably lost due to the effect of the epoxy resin.

The metal salt of an organic acid of the present invention is a metal salt of an organic acid of the carboxylic acid type. The organic acid of the carboxylic acid type constituting the metal salt of the 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 aromatic organic acids include benzoic acid, phenylacetic acid, hydrocinnamic acid, phenylbutyric acid, phenylvaleric acid, phenylcaproic acid, phenylenanthic 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, etc. 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 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. , 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 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 the organic acid is used alone or in combination.
These metal salts of organic acids exhibit an effect when used in combination with the epoxy resin described above. 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 chlorinated polyethylene and / or chlorosulfonated polyethylene cross-linked composition of the present invention may further contain, if necessary, a compounding agent for rubber, for example, a dehydrochlorination scavenger, an antioxidant, a tackifier, a plasticizer. , A softener, a reinforcing agent, a bulking agent, and the like. 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 the ordinary crosslinking temperature of rubber.
It is performed at a temperature of 00 ° C. or higher.

[0016]

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, carbon tetrachloride 1
According to 7.5 liters and JIS K-6760, 2.8 kg of high-density polyethylene having a melt index of 5.2 measured at a temperature of 190 ° C. under a load of 2160 g was added.
The temperature was raised to 100 ° C. with stirring, and the high-density polyethylene was dissolved in carbon tetrachloride. Next, chlorine gas was blown in from the lower part of the reactor at a rate of 2.8 liters / min.
A weight percent solution of chlorinated polyethylene in carbon tetrachloride was obtained.
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 Examples, Comparative Examples, and formulations used in Comparative Examples. First, using an 8 inch roll manufactured by Toyo Seiki Seisaku-Sho, Ltd., the compositions of Examples, Comparative Examples and Reference Examples were kneaded, and the kneaded product 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, it can be seen that Examples are higher in tensile strength, smaller in rate of change by air heating aging test, and smaller in volume change by immersion test than Comparative Example, indicating that they are sufficiently crosslinked. You. Further, Example is Reference Example-1.
3 shows the test results comparable to those of the crosslinked rubber sheet obtained by crosslinking with the thiol derivative of trithiocyanuric acid and dicumyl peroxide of Reference Example 2.

[0021]

[Table 1]

[0022]

As is apparent from the above description, the chlorine-containing rubber crosslinked composition of the present invention comprising a chlorinated polyethylene and / or chlorosulfonated polyethylene, an epoxy resin and a metal salt of an organic acid is chlorinated polyethylene and It can be seen that the composition is a novel composition which crosslinks chlorosulfonated polyethylene and can be sufficiently used for practical use.

Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08L 23/34 C08L 23/34 // (C08L 23/28 63:00) (C08L 23/34 63:00) (56) References JP JP-A-4-106905 (JP, A) JP-A-4-85351 (JP, A) JP-A-61-251642 (JP, A) JP-A-4-328145 (JP, A) JP-A-4-275348 (JP) , A) JP-A-61-252 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/28 C08L 23/34 C08L 19/00 C08L 63/00 C08K 5/098 C08J 3/24

Claims (1)

(57) [Claims] A chlorine-containing rubber crosslinked composition comprising 1 to 30 parts by weight of an epoxy 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.