JP2699479B2 - Rubber laminate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a rubber laminate. More specifically, the present invention relates to a rubber laminate comprising a chlorinated polyethylene composition and a sulfur-vulcanizable diene rubber composition. More particularly, the present invention relates to a rubber laminate in which the layers of a chlorinated polyethylene composition and a sulfur-vulcanizable diene rubber composition are extremely strongly vulcanized and bonded.

And the rubber laminate of the present invention is a rubber roofing, a rubber roll, a rubber lining, a rubber mat, a rubber cable,
Used as rubber products such as rubber magnets.

(Conventional technology) Chlorinated polyethylene is a rubber having excellent chemical and physical properties such as weather resistance, heat aging resistance, ozone resistance, flame retardancy, and lightness. On the other hand, various sulfur-vulcanizable diene rubbers have higher rubber elasticity, lower compression set, higher tear resistance, higher flex crack resistance, or lower gas permeation than chlorinated polyethylene. It has features,
Poor weather resistance, heat aging resistance, ozone resistance, flame retardancy, light color, etc. From this, in order to obtain a rubber product having the excellent properties of sulfur-vulcanizable diene rubber and the excellent properties of chlorinated polyethylene, chlorinated polyethylene was used as the outer protective layer, BACKGROUND ART Rubber products of a rubber laminate having a base rubber as an inner layer have been manufactured. Also, in order to impart special physical or mechanical properties to rubber products, rubber laminate products comprising multiple layers of a chlorinated polyethylene layer and a sulfur-vulcanizable diene rubber layer have been manufactured.

Generally, the vulcanization system of chlorinated polyethylene is vulcanized with a thiourea vulcanization accelerator and a metal compound, an organic peroxide and a metal compound, or a triazine thiol compound and a metal compound. The sulfur-vulcanizable diene rubber is vulcanized using a system of sulfur and a vulcanization accelerator for rubber or an organic peroxide. In bonding and vulcanizing this chlorinated polyethylene and sulfur-vulcanizable diene rubber, in any vulcanization system such as a vulcanization system of chlorinated polyethylene and a vulcanization system of sulfur-vulcanizable diene rubber, The peel strength between layers after vulcanization bonding is extremely weak.

Therefore, the chemical, physical or mechanical properties of the rubber product are inferior due to the delamination between the layers of the rubber laminate, and no satisfactory rubber laminate has been obtained. For this reason, at present, there is a strong demand for the appearance of a rubber laminate having extremely high peel strength between layers after the chlorinated polyethylene layer and the sulfur-vulcanizable diene-based rubber layer are bonded by vulcanization.

(Problems to be Solved by the Invention) The inventors of the present invention have conducted intensive studies in order to solve the above-mentioned problems and respond to requests, and as a result, have found that the chlorinated polyethylene composition and the sulfur-vulcanizable diene rubber composition of the present invention have And a rubber laminate comprising the same.

The present invention provides a rubber laminate having an extremely strong peel strength between the chlorinated polyethylene layer and the sulfur-vulcanizable diene rubber layer, the peel strength between the layers being extremely weak as described above. To provide.

(Means for Solving the Problems) A feature of the present invention is a composition obtained by blending an organic peroxide and a metal compound with chlorinated polyethylene, and an inorganic and / or organic compound having a reducing action on a sulfur-vulcanizable diene rubber. A rubber laminate comprising a composition containing a metal salt and a metal compound.

 Hereinafter, the present invention will be described in detail.

The chlorinated polyethylene used in the present invention,
It is obtained by introducing chlorine into polyethylene, ethylene-butene-1 copolymer, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer or the like to form a rubber. The introduction of chlorine suspends the polymer powder or particles in water,
Chlorine is introduced by blowing chlorine gas or by dissolving the polymer in an organic solvent such as carbon tetrachloride and blowing chlorine gas. The amount of chlorine is not particularly limited as long as the chlorinated polyethylene is rubbery.
15 to 55% by weight, preferably 30 to 40% by weight, of the chlorinated polyethylene is in rubbery form.

Examples of the organic peroxide blended in the chlorinated polyethylene of the present invention include ketone peroxide, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxyesters, such as methyl ethyl ketone peroxide and cyclohexane peroxide. , Ketone peroxide, t-butyl hydroperoxide, cumene hydroperoxide, di-
Isopropylbenzene height drop peroxide, P-
Methane hydroperoxide, 2,5-di-methylhexane-2,5-dihydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide,
Di-cumyl peroxide, 2,5-di-methyl-di (t
-Butylperoxy) hexane, acetyl peroxide, propionyl peroxide, iso-butyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, 3,3,5-tri-methylhexanoyl peroxide Oxide, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-di-chlorobenzoyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyvivalate, t- Butylperoxylaurate and the like. These are blended with the chlorinated polyethylene alone or as a mixture. The amount of the organic peroxide to be blended is 0.1 to 25 parts by weight, preferably 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight per 100 parts by weight of the chlorinated polyethylene.
Used in the range of parts by weight. When the amount of the organic peroxide is less than 0.1 part by weight, the vulcanization of the chlorinated polyethylene requires a long time, and is not practical. If the amount is more than 25 parts by weight, the mechanical properties of the chlorinated polyethylene are inferior and are not preferred.

The metal compound compounded in the chlorinated polyethylene captures hydrochloric acid released during the vulcanization of the chlorinated polyethylene, and includes a metal oxide, an organic lead compound, a metal hydroxide,
There are fatty acid metal soaps, such as magnesium oxide, calcium oxide, zinc oxide, lead monoxide, lead tetroxide, tribasic lead maleate, dibasic lead phthalate, tribasic lead sulfate, and dibasic zinc oxide. Examples include lead phosphate, calcium hydroxide, sodium stearate, magnesium stearate, calcium stearate, and lead stearate. These may be used alone or as a mixture. The compounding amount is 0.1 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the chlorinated polyethylene. The amount to be added is an amount generally used for chlorinated polyethylene.

The sulfur vulcanizable diene rubber of the present invention is generally a sulfur vulcanizable diene rubber vulcanized with sulfur and a vulcanization accelerator for rubber, and includes a natural rubber and a conjugated double bond. There are polymers and copolymers made mainly of such monomers, such as isoprene rubber, styrene-butadiene rubber, butadiene rubber, isobutylene-isoprene rubber, acrylonitrile-butadiene rubber, and acrylate-butadiene rubber. The sulfur-vulcanizable diene rubber used in the present invention is vulcanized with sulfur and a vulcanization accelerator for rubber.

The sulfur compounded in the sulfur-vulcanizable diene rubber of the present invention is sulfur or a sulfur compound used as a vulcanizing agent for the diene rubber, such as powdered sulfur, sulfur white, precipitated sulfur, and colloidal sulfur. , Sulfur chloride, sulfur dichloride, morpholine disulfide, alkyl phenol disulfide and the like. These are used alone or in combination. The compounding amount is 0.1 to 5 parts by weight per 100 parts by weight of the sulfur-vulcanizable diene rubber. This amount is an amount generally used for sulfur-vulcanizable diene rubber.

Further, the rubber vulcanization accelerator compounded with a sulfur-vulcanizable diene rubber is a vulcanization accelerator for rubber that is extremely commonly used for sulfur-vulcanizable diene rubber together with sulfur. Hexamethylene tetramine, diphenyl guanidine, 2-mercapto benzothiazole, dibenzothiazyl disulfide, N-cyclohexyl benzothiazyl-2-sulfenamide, N-oxy diethylene benzothiazyl-2-sulfenamide, tetramethyl thiuram disulfide , Tetraethyl
Examples include thiuram disulfide, tetramethyl thiuram monosulfide, zinc dimethyl dithiocarbamate, zinc zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, zinc butyl xanthate, and the like. These are used alone or in combination. The compounded amount is 100 sulfur-curable diene rubber.
0.1 to 5 parts by weight per part by weight is blended. This amount is an amount generally used for sulfur-vulcanizable diene rubber.

The inorganic and / or organic metal salt having a reducing action, which is compounded in the sulfur-vulcanizable diene rubber of the present invention, can give an electron to another substance or deprive another substance of an oxygen atom. Inorganic and / or organic metal salts such as aluminum powder, iron powder, cobalt powder, zinc powder, copper powder,
Tin powder, aluminum chloride, manganese chloride, iron chloride, cobalt chloride, zinc chloride, copper chloride, manganese chloride, tin chloride,
Sodium bisulfite, sodium sulfite, sodium sulfate, aluminum sulfate, iron sulfate, zinc sulfate, copper sulfate,
Examples include lead oxalate, diethyl aluminum, diethyl zinc, diethyl cadmium, diethyl chloroboron, triethyl boron, triethyl aluminum, iron naphthenate, cobalt naphthenate, copper naphthenate, and lead naphthenate. These are used alone or in combination. The compounding amount is 0.0 per 100 parts by weight of the sulfur-vulcanizable diene rubber.
1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight is blended. If less than 0.01 parts by weight,
The effect of the inorganic and / or organic metal salt having a reducing action is small, and does not exhibit strong vulcanized adhesion. Even if it is added in an amount exceeding 20 parts by weight, it does not exceed the strong vulcanization adhesion in the case of being added in the range of 0.01 to 20 parts by weight, and is not worth mixing.

The metal compound compounded in the sulfur-vulcanizable diene rubber is the same as the metal compound compounded in the chlorinated polyethylene described above, and the hydrochloric acid generated when the chlorinated polyethylene is vulcanized and bonded. Is formulated to capture The amount to be compounded is 0.1 to 20 parts by weight.If the amount is less than 0.1 part by weight, sufficient hydrochloric acid is not captured, so that the peel strength between the layers to be vulcanized and bonded and the mechanical strength of the diene rubber capable of sulfur vulcanization are reduced. Is shown. Even when the amount is more than 20 parts by weight, the dehydrochlorination trapping effect is the same as the effect in the range of 0.1 to 20 parts by weight, and 2
There is no value in adding more than 0 parts by weight, and conversely, the mechanical properties of the diene rubber decrease, which is not preferable.

The chlorinated polyethylene composition of the present invention and a sulfur-vulcanizable diene rubber composition may optionally contain a rubber compounding agent,
For example, vulcanizing agents, vulcanization accelerators, antioxidants, tackifiers,
A plasticizer, a softener, a reinforcing agent, an extender and the like are blended. The method for producing the rubber laminate of the present invention is not particularly limited, and each composition is kneaded and compounded by a kneading machine such as a kneading roll machine, an internal mixer, and a double-arm kneader. Next, they are laminated by a pressure molding machine, for example, a roll molding machine, an extrusion molding machine, a compression molding machine, a calendar roll of an injection molding machine, and the like, and the obtained rubber laminate is vulcanized at a high temperature, for example, a vulcanizing can, hot air Molded and / or vulcanized by a circulation vulcanizer, a compression vulcanizer, an injection vulcanizer, a fluidized bed vulcanizer and the like.

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

Chlorinated polyethylene used in Examples and Comparative Examples,
It was manufactured by the following method.

In a 30 liter reactor, 17.5 liters of carbon tetrachloride,
According to JIS K-6760, high-density polyethylene with a melt index of 5.2 measured at a temperature of 190 ° C and a load of 2160 g
2.8 kg was added, and the temperature was raised to 100 ° C. with stirring to dissolve the high-density polyethylene in carbon tetrachloride. Next, add chlorine gas to 2.
Blowing was performed from the lower part of the reactor at a rate of 8 liters / minute to obtain a chlorinated polyethylene carbon tetrachloride solution 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 4 and Comparative Examples-1 to 4 Table 1 shows the formulations used in Examples and Comparative Examples.
The composition A of the examples and comparative examples in the table is a composition of chlorinated polyethylene, and the composition B is a composition of a diene rubber capable of sulfur vulcanization. Formulation A and Formulation B were kneaded using an 8-inch roll manufactured by Toyo Seiki Seisaku-sho, Ltd.
And cut into 15 cm long and 15 cm wide sheets. The cut sheet of the composition A and the sheet of the composition B are overlapped, and the laminate composed of the composition A and the composition B is placed in a vulcanizing mold having a height of 15 cm, a width of 15 cm, and a thickness of 2 mm, and compression molding vulcanization is performed. Vulcanization bonding was performed at a pressure of 50 kg / cm 2 and a temperature of 160 ° C. for 30 minutes using a machine.

Next, the obtained rubber laminate was cut into a 1-inch width tank shape, and in accordance with JIS K6301, a tensile speed of 50 cm / min.
A 180 ° peel test was performed at a test temperature of 23 ° C. Examples 1-4
The test results of Comparative Examples 1 to 4 are shown in Table 1.

As can be seen from Table 1, the peel strength between the layers in Examples -1 to 4 is larger than that in the comparative example, and the layers between the chlorinated polyethylene and the sulfur-vulcanizable diene rubber laminate are extremely strong. It can be seen that the adhesive is vulcanized.

Comparative Example-1 shows the peel strength of the rubber laminate obtained by removing the inorganic metal salt having a reducing action (iron sulfate) from Formulation B of Example-1. Comparative Example-2 shows the reduction strength of Formulation B of Example-2. It is the peel strength of the rubber laminate excluding the inorganic metal salt (copper sulfate) having an effect. Comparative Example-3 shows the peel strength of the rubber laminate obtained by removing the inorganic metal salt having a reducing action (copper chloride) from Formula B of Example-3. Comparative Example-4 is a rubber laminate in which the organometallic salt (copper naphthenate) was removed from Formulation B of Example-4, and the vulcanization system of sulfur and the rubber vulcanization accelerator was an organic peroxide system. The peel strength of the body. That is, as shown in the embodiment,
Chlorinated polyethylene is used as the organic peroxide vulcanization system, sulfur vulcanizable diene rubber is used as the commonly used sulfur and rubber vulcanization accelerator system, and inorganic and / or organic compounds having a reducing action. By blending the metal salt and the metal compound of the present invention, a rubber laminate in which the interlayers intended for the present invention are extremely strongly vulcanized and bonded can be obtained.

(Effects of the Invention) As is clear from the above description, the rubber laminate of the present invention is characterized in that the interlayer between the chlorinated polyethylene composition and the sulfur-vulcanizable diene rubber composition which did not show strong vulcanization adhesion was obtained. It can be seen that this is a rubber laminate having extremely strong vulcanization bonding and strong peel strength between layers. From this, rubber laminate with excellent chemical, physical or mechanical properties,
Alternatively, a rubber laminate having a special function can be provided to the market.

Claims (1)

(57) [Claims] 1. A composition comprising 0.1 to 25 parts by weight of an organic peroxide and 0.1 to 30 parts by weight of a metal compound per 100 parts by weight of chlorinated polyethylene, and 0.1% by weight of sulfur per 100 parts by weight of a sulfur-vulcanizable diene rubber. ~ 5 parts by weight, vulcanization accelerator for rubber 0.1 ~
A rubber laminate comprising a composition containing 5 parts by weight, 0.01 to 20 parts by weight of an inorganic and / or organic metal salt having a reducing action, and 0.1 to 20 parts by weight of a metal compound.