JPH02191649A - Chlorine-containing rubber composition - Google Patents

Abstract

PURPOSE:To provide a chlorine-containing rubber composition not lowering ozone resistance even on the direct steam vulcanization of a molded product thereof by adding an organic acid metal salt to a chlorinated polyethylene or chlorosulfonated polyethylene. CONSTITUTION:A chlorine-containing rubber composition is obtained by compounding and kneading (A) 100 pts.wt. of a chlorinated polyethylene (e.g. chlorinated ethylene-vinylacetate copolymer) or a chlorosulfonated polyethylene (e.g. chlorosulfonated ethylene-butene-1 copolymer) having a chlorine content of 15-55wt.%, preferably 30-40wt.%, with (B) 0.1-20 pts.wt., preferably 0.5-10 pts.wt., further preferably 1-5 pts.wt., of a carboxylic acid type organic acid metal salt (e.g. lead naphthenate), further a hydrochloric acid-capturing agent (e.g. magnesium oxide), a vulcanizing agent, a vulcanization accelerator and other rubber additives (e.g. an antiaging agent, a tackifier, a plasticizer).

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a chlorine-containing rubber composition. Specifically, the present invention relates to a chlorine-containing rubber composition with excellent ozone resistance for rubber products that are directly steam vulcanized.

The chlorine-containing rubber composition of the present invention is widely used in rubber products such as rubber hoses, rubber cables, rubber mats, rubber roofing, and rubber belts.

(Prior art) Generally, rubber products are made by adding rubber compounding agents such as vulcanizing agents, vulcanization accelerators, anti-aging agents, tackifiers, plasticizers, softeners, reinforcing agents, thickeners, etc. to rubber. Mixing is performed using a kneading machine such as a kneading roll machine, internal mixer, double-arm kneader, etc., and then a molding machine such as a roll molding machine, an extrusion molding machine, a compression molding machine, an injection molding machine, a calender roll, etc. The obtained rubber molded body is vulcanized in a vulcanizer under high temperature, such as a vulcanizer, a hot air circulation vulcanizer, a compression mold vulcanizer, an injection mold vulcanizer, a fluidized bed vulcanizer, etc. to obtain rubber products.

Rubber products made of chlorinated polyethylene or chlorosulfonated polyethylene can also be obtained by the above manufacturing method, but in the above manufacturing method, a rubber compounding agent is blended with chlorinated polyethylene or chlorosulfonated polyethylene, and then a molding machine is used. Rubber products obtained by direct steam vulcanization, in which the molded body is directly exposed to high-temperature, high-pressure steam, have extremely low resistance to ozone. However, rubber products that require ozone resistance are IJ,? The reality is that steam vulcanization does not even achieve this.

This direct steam vulcanization method is an extremely advantageous method for vulcanizing long rubber molded bodies, so chlorinated polyethylene or chlorosulfonated polyethylene can be directly steam vulcanized to reduce its resistance to ozone to 0 (0). However, there is a strong desire for a rubber composition that does not contain chlorine.

(Problems to be Solved by the Invention) As a result of intensive research to solve the above problems and meet the demands, the present invention has proposed the chlorine-containing rubber composition of the present invention.
It is something to do.

(Means for Solving the Problems) The object of the present invention is to provide a chlorine-gold-platinum rubber composition comprising chlorinated polyethylene or chlorosulfonated polyethylene and a metal salt of an organic acid. chlorine iv t
The rubber molded product of the '4 rubber composition is directly steam vulcanized and the resistance to ozone does not decrease even in C.

The present invention will be explained in detail below.

The chlorinated polyethylene used in the present invention is polyethylene, ethylene-butene-1 octapolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, etc., which are made into rubber by introducing chlorine into them. To introduce chlorine, either suspend the powder or particles of the above polymer in water and chlorinate it by blowing chlorine gas into it, or dissolve the polymer M in an organic solvent such as carbon tetrachloride and chlorinate it by blowing chlorine gas into it. However, chlorine is introduced. The amount of chlorine in chlorinated polyethylene is not particularly limited as long as it is rubber-like, but if the chlorine port is 1
5-55% by weight, preferably 30-40L [1%] of chlorinated polyethylene in rubbery form.

In addition, the chlorosulfonated polyethylene used in the present invention refers to rubber produced by introducing chlorine and chlorosulfonyl groups into polyethylene, ethylene-butyne-1 copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer, etc. It is made into a shape. In order to introduce chlorine and chlorosulfonyl groups, the above polymer is dissolved in an organic solvent such as carbon tetrachloride, chlorine gas is blown in to chlorinate it, and at the same time, chlorosulfonyl is added and reacted to introduce chlorine and chlorosulfonyl groups. be done. A commercially available grade of chlorosulfonated polyethylene is TO5O manufactured by Tosoh Corporation.
-CSM's TS-530, TS430, TS-930,
There are TS-740, TS-320, TS-220, etc.

The metal salt of an organic acid blended into the chlorinated polyethylene or chlorosulfonated polyethylene of the present invention is a metal salt of a carboxylic acid type organic acid, which is a carboxylic acid type organic acid constituting the metal salt of the organic acid. These include saturated fatty acids and unsaturated fatty acids having 6 or more carbon atoms, chain organic acids having less than 6 carbon atoms, aromatic #1 acids, and cyclic organic acids.

Examples of saturated fatty acids having 6 or more carbon atoms include caproic acid,
enanthic acid, caprylic acid, pelargonic acid, capric acid,
Unsaturated fatty acids with 6 or more carbon atoms such as undecanoic acid, lauric acid, myristic acid, valmitic acid, valmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melisic acid, etc., such as hexenoic acid , heptenoic acid, octenoic acid, nonenoic acid, decylenic acid, undecanoic acid, dodecylenic acid, valmiceric acid, oleic acid, lysyllic acid, petroselic acid, vaccenic acid, linoleic acid, lysyllic acid, eleostearic acid, lycanic acid , valinaric acid, crilic acid, cadreic acid, arachidonic acid, motolytic acid, erucic acid, ceracoleic acid, etc., and dibasic and tribasic acid types of these fatty acids.

Examples of chain organic acids having less than 6 carbon atoms include phosphoric acid, acetic acid,
Monobasic acids such as propionic acid, acetic 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, acrylic acid, etc. type chain organic acids and their dibasic and tribasic acid forms fatty acids.

Examples of aromatic hexagroup organic acids include benzoic acid, phenylacetic acid,
Hydrocinnamic acid, phenylbutyric acid, phenylcaproic acid,
Phenylcaproic acid, phenylenanthate, phenylcaprylic acid, phenylpelargonic acid, phenylcapric acid, benzoyl acrylic acid, phenylcyclohexylic acid,
Cyclic organic acids such as phenylbenzoic acid, phenylundecanoic acid, naphthoic acid, phthalic acid, mehalitic acid, toluic acid, salicylic acid, acetylsalicylic acid, cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, etc. acid,
Cyclohebutanecarboxylic acid, heptylcyclopentyl acetate, octylcyclopentyl acetate, nonylcyclopentyl acetate, undecylcyclopentyl acetate, pentylcyclohexyl acetate, heptylcyclohexyl acetate, nonylcyclohexyl acetate, undecylcyclohexyl acetate,
Octylcyclopentyl acetate, undecylcyclopentyl acetate, pentacyclopentyl acetate, hexacyclobentyl acetate, decylcyclohexylpropionic acid, dodecylcyclohexylpropionic acid, tetradecylcyclohexylpropionic acid, cyclohexylpropionic acid, cyclohexyl acetate, cyclo Aromatic organic acids such as hexylcaproic acid, cyclohexylcapric acid, cyclohexyllauric acid, naphthenic acid, camphonanic acid, malebrolic acid, malebreastic acid, tucarpic acid, methylene octadecenoic acid, dimer acid, resin acid, etc. Examples include cyclic organic acids.

The metal that constitutes the metal salt of white organic acid is a combination of multiple atoms &+
Among the transition element metals showing 1i, the periodic table 47th, '
J 10j Copper of group ■ subgroup, germanium of group ■, titanium, vanadium, chromium, manganese of group V to group ■ subgroup, iron, cobalt, nickel of group ■, subgroup A of group 5 of J 10j Tin, refers to lead in Group 6, Group A, Subgroup A.

The term "metal salt of an organic acid" as used in the present invention refers to a compound composed of the above-mentioned organic acid and a metal.

These metal salts of white acid are added alone or in combination to chlorinated polyethylene or chlorosulfonated polyethylene. The amount to be blended is 0.000 parts per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene.
It is blended in an amount of 1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, and more preferably 1 to 5 parts by weight. If it is less than 0.1 part by weight, the effect on ozone resistance is small and has no practical value, and if it exceeds 20 ir1m part, the puffiness and physical properties of chlorinated polyethylene or chlorosulfonated polyethylene will be inferior, which is not preferable. .

The chlorine-containing fi rubber composition of the present invention further includes a FA-free acid t which captures hydrochloric acid generated from chlorinated polyethylene or chlorosulfonated polyethylene during direct steam vulcanization.
117 scavengers and/or vulcanizing agents, such as metal oxides, aircraft compounds, metal hydroxides, fatty acid metal soaps, such as magnesium oxide, calcium oxide, zinc oxide, -
Lead oxide, trilead tetraoxide, tribasic lead sulfate, dibasic lead phosphite, calcium hydroxide, sodium stearate, magnesium stearate, calcium stearate, and the like are appropriately blended. In addition, organic peroxides, triazinethiol compounds, thiourea compounds, thiuram compounds, polyamine compounds, polyfunctional methacrylate-1, etc. can be used as vulcanizing agents and/or vulcanization accelerators for chlorinated polyethylene or chlorosulfonated polyethylene. type compounds, polyhydric alcohol/methacrylate and acrylate type compounds, other vulcanizing agents and/or vulcanization accelerators, such as t-butyl hydroperoxide, dicumyl peroxide, 2
5-di-methyl-2,5-di(t-butylperoxy)hexane, 1. ．． 3.5-trithiocyanuric acid, 1
-methoxy-3,5-dimercaptotriazine, 1-hexylamino-3,5-dimercaptotriazine, ethylenethiourea, dibutylthiourea, diethylthiourea, dipentamethylene thiuram tetrasulfide, tetramethyl thiuram disulfide, Hexamethylene diamine, hexamethylene diamine carbamate, ethylene diamine carbamate, ethylene glycol dimethacrylate, methylolpropane trimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, trimethylolpropane triacrylate,
Trimethylolbroban trimethacrylate, N,
N'm-phenylene dimaleimide, triallylic isocyanurate, etc. are appropriately blended.

The chlorine-containing rubber composition of the present invention may contain other rubber compounding agents, such as anti-aging agents, tackifiers, plasticizers, softeners, reinforcing agents, fillers, etc., as necessary. The method for producing the chlorine-containing rubber composition of the present invention is not particularly limited, and may be kneaded and compounded using a kneading machine such as a kneading roll machine, an internal mixer, or a double-arm kneader. Next, it is molded using a pressure molding machine, such as a roll molding machine, an extrusion molding machine, a compression molding machine, a calender roll, etc., and the obtained molded product is placed in a vulcanizing can and steam-vulcanized at 1°L tD.

(Effects of the Invention) As is clear from the explanation below, the chlorine 3a rubber composition of the present invention is composed of chlorinated polyethylene or chlorosulfonated polyethylene mixed with a metal salt of an organic acid, Direct steam vulcanized rubber products with excellent ozone resistance can be obtained.

(Examples) Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

The chlorinated polyethylene used in Examples and Comparative Examples was manufactured by the following method.

17.5 liters of carbon tetrachloride and a temperature of 19 C1 according to JIS K-6760 were placed in a 0 liter reactor.
'Add 2.8g of high-density polyethylene with a melt index of 5.2 measured at a C1 load of 2160g and heat to 180℃ while stirring! The polyethylene was dissolved in carbon tetrachloride at a temperature of 1°C. Next, chlorine gas was blown from the bottom of the reactor at a rate of 2.8 l/min until the chlorine content was 3.
5ffl! % chlorinated polyethylene in carbon tetrachloride solution was obtained. Carbon tetrachloride was removed from this solution using a drum dryer to obtain solid chlorinated polyethylene.

Examples 1 to 6 and Comparative Examples 1 to 3 Table 1 shows the formulations used in the Examples and Comparative Examples. First, the Examples and Comparative Examples were mixed and kneaded using an 8-inch roll made by Toyo Seiki Seisakusho, and then extruded for rubber with a cylinder length of 5 C1 cm and a cylinder inner diameter of 5 cm made by Imanaka Kikai Kogyo Co., Ltd. Extruded with a machine to a thickness of 2 mm,
lll2c mouth] into a ribbon shape, which is 20cm long.
Cut to rn. The obtained 113 bodies were placed in a 600 mm internal diameter Mfli manufactured by Clutch Door Co., Ltd. so as to be exposed to direct steam, and the steam pressure was 3° g 1 (g/c).
Vulcanization was carried out at a temperature of 150° C. for 20 minutes. The obtained vulcanizate was made into a sheet with a width of 16 m rn s and a length of 115 m.
It was cut into 2 mm pieces to prepare test pieces for ozone exposure. A dynamic ozone test was conducted on this test piece using an ozone weather meter model 〇MS-' U-type manufactured by Toyo Rikako Co., Ltd. Test conditions were 3096 extensions, 300 extensions/
min, ozone concentration 501) p 11m, temperature 40°C,
The exposure time was 48 hours. The test results are shown in Table-1. The dynamic ozone crack state in Table 1 is JIS K 63
Judgment was made according to 01.

As shown in Table 1, Examples are the dynamic ozone test results of the chlorine-gold platinum rubber composition, which is the object of the present invention, in which a metal salt of white organic acid is blended with chlorinated polyethylene or chlorosulfonated polyethylene. The Comparative Example is the dynamic ozone test result of a composition obtained by excluding the metal salt of an organic acid from the Example. As can be seen from Table 1, it can be seen that the examples have better ozone resistance than the comparative examples.

Claims (1)

[Claims] (1) 0.1 metal salt of organic acid per 100 parts by weight of chlorinated polyethylene or chlorosulfonated polyethylene
A chlorine-containing rubber composition comprising ~20 parts by weight.