JPH06246876A - Rubber laminate - Google Patents

Abstract

PURPOSE:To obtain a rubber laminate, which has excellent interfacial adhesion, thermal aging resistance, low-temperature weatherability and resistance to oil. CONSTITUTION:The rubber laminate concerned is a specific chlorinated ethylene.alpha-olefin copolymer rubber consisting of a layer made of triazine compound-containing copolymer rubber (A) and layer made of ethylene.alpha-olefin copolymer rubber (B) and its vulcanized matter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate of a specific chlorinated ethylene / α-olefin copolymer rubber and ethylene / α-olefin copolymer rubber and a method for producing the same. The present invention relates to a rubber laminate having excellent interfacial adhesion, heat aging resistance, cold resistance, weather resistance, and oil resistance, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, development of a rubber material having excellent heat aging resistance, weather resistance, oil resistance and cold resistance for rubber parts for automobiles, industrial rubber parts, etc. has been studied, but it is still insufficient. Things have not been obtained. Regarding chlorinated ethylene / α-olefin copolymer rubber, it is a rubber excellent in heat aging resistance, weather resistance, and oil resistance, but it has a drawback of poor cold resistance.On the other hand, ethylene / α-olefin copolymer rubber is Although it is excellent in heat aging resistance and cold resistance, it has a drawback that it is inferior in weather resistance and oil resistance.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a rubber material which is simultaneously excellent in heat aging resistance, weather resistance, oil resistance and cold resistance as a rubber laminate.

[0004]

SUMMARY OF THE INVENTION The rubber laminate according to the present invention has a chlorine content of 20 to 40% by weight and a Muni-viscosity [ML.
_{1 + 4} (121 ° C)] is 10 to 190, and a chlorinated ethylene / α-olefin copolymer rubber (A) layer, and ethylene /
A rubber laminate comprising an α-olefin copolymer rubber (B) layer, the chlorinated ethylene / α-olefin copolymer rubber (A) layer containing a triazine compound.

[Detailed Description of the Invention] The rubber laminate according to the present invention will be specifically described below. Chlorinated Ethylene / α-Olefin Copolymer Rubber (A) The chlorinated ethylene / α-olefin copolymer rubber used in the present invention has a chlorine content of 20 to 40% by weight.
Two-viscosity [ML _{1 + 4} (121 ° C.)] is 10 to 190.

The α-olefin of the ethylene / α-olefin copolymer before chlorination preferably has 3 to 10 carbon atoms. Especially propylene, 1-butene, 4-
Methyl-pentene-1, hexene is preferred. Of these, 1-butene is most preferred. The ratio of ethylene and α-olefin is ethylene / α-olefin = on a molar basis.
It is preferably 75/25 to 95/5.

The chlorinated ethylene / α-olefin copolymer rubber is obtained by chlorinating the ethylene / α-olefin copolymer obtained above.

The chlorination of the above-mentioned copolymer is carried out, for example, by pulverizing the copolymer to make fine particles, and making the fine particles into an aqueous suspension state.
A method of contacting with molecular chlorine at a temperature of about 60 to 90 ° C.,
A method in which a copolymer is dissolved in a solvent stable to chlorine such as carbon tetrachloride, chloroform and tetrachloroethylene and brought into contact with molecular chlorine in a uniform solution state, or N-chloroacetamide, N-chloro A chlorine compound such as succinimide or 1,3-dichloro-5,5-dimethylhydantoin is uniformly kneaded into the copolymer with a roll or Banbury, and heated to a temperature at which chlorine is liberated. Particularly preferred is a method in which chlorine is blown in the presence of a radical initiator in a halogen-based solvent such as carbon tetrachloride or chloroform.

After the chlorination reaction, it is treated as follows. In case of chlorination in aqueous suspension, chlorinated ethylene
The α-olefin copolymer rubber is washed with water to remove molecular chlorine and hydrogen chloride produced as a by-product, and dried. In the case of chlorination in a solution state, the reaction solution is put in an excess solvent of a chlorinated ethylene / α-olefin copolymer rubber such as methanol, the precipitate is filtered, and washed with this solvent. dry.

The chlorinated ethylene / α-olefin copolymer rubber used in the present invention has a chlorine content of 20 to 40% by weight, preferably 25 to 35% by weight, and chlorination is carried out within this range. . Also, the Mooney viscosity [ML
_{1 + 4} (121 ℃)] is 10 to 10 from the viewpoint of physical properties and workability.
190, preferably 20-150, more preferably 3
Those of 0 to 120 are used. The chlorinated ethylene / α-olefin copolymer rubber (A) of the present invention comprises the above chlorinated ethylene / α-olefin copolymer rubber containing a triazine compound.

Triazine Compound The triazine compound used in the present invention is represented by the following formula 1.
Triazine thiol represented by.

[0012]

[Chemical 1] (In the formula, R ¹ represents —NR ² R 3, —OR ² or —SR ² , wherein R ² and R ³ are each a hydrogen atom, an unsubstituted or substituted alkyl group, or an unsubstituted or substituted aryl group. Shall represent a group.)

Specific examples of the triazinethiol represented by the above general formula include triazine-2,4,6-
Trithiol, 2-dibutylaminotriazine-4,6
-Dithiol, 2-phenylaminotriazine-4,6
-Dithiol, 2-hexylaminotriazine-4,6
-Dithiol, 2-diethylaminotriazine-4,6
-Dithiol, 2-butoxytriazine-4,6-dithiol and the like can be mentioned. The preferred triazine thiol is 2-dibutylaminotriazine-4,6-dithiol.

The content of these triazine compounds in the chlorinated ethylene / α-olefin copolymer rubber (hereinafter sometimes referred to as compounding amount) is usually chlorinated ethylene / α-olefin.
3.0 × 1 for 100 parts by weight of olefin copolymer rubber
0 ⁻⁴ mol to 3.0 × 10 ⁻² mol parts by weight, preferably 1.
It is compounded in a proportion of 0 × 10 ⁻³ mol to 1.5 × 10 ⁻² mol parts by weight, and more preferably 2.0 × 10 ⁻³ mol to 1.0 × 10 ⁻² mol parts by weight. The mixing method is not particularly limited,
Open rolls commonly used in the production of compounded rubber,
It may be mixed at the time of manufacturing the compounded rubber by a kneading device such as a Banbury mixer. The blended triazine compound contributes to the interlayer vulcanization adhesion of the rubber laminate and acts as a vulcanizing agent.

Ethylene / α-olefin copolymer rubber (B) The ethylene / α-olefin copolymer rubber used in the present invention is a copolymer of ethylene and α-olefin,
As the α-olefin, propylene, 1-butene, 1
-Hexene etc. can be illustrated. Propylene is preferred. The ethylene content is 50 to 95 mol%, preferably 6
0-92 mol% and the Muni-viscosity [ML _{1 + 4} (12
1 to 90 ° C.] is 10 to 190, preferably 20 to 180, more preferably 30 to 150.

Further, the ethylene / α-olefin copolymer rubber preferably contains at least one polyene component. Examples of the polyene component include chain non-conjugated dienes such as 1,4-hexadiene and 7-methyl-1,6-octadiene, cyclic non-conjugated dienes such as 5-ethylidene-2-norbornene and dicyclopentadiene. it can. The preferred polyene is 5-ethylidene-
2-norbornene.

These non-conjugated dienes are copolymerized to have an iodine value of 3 to 30, preferably 5 to 20.

The above-mentioned ethylene / α-olefin copolymer rubber is produced by a method known per se, for example, as described in "Ethylene / Propylene Rubber" (Taisei Co., Ltd.), which is a synthetic rubber processing technology document.

Further, when the ethylene / α-olefin copolymer rubber is blended with a white filler containing silicon dioxide and chloropropyltrimethoxysilane, the adhesive strength after vulcanization at the interlayer interface of the rubber laminate of the present invention is further improved. It is desirable because it improves. The compounding method is not particularly limited, but it may be mixed at the time of compound rubber production by an open roll, Banbury mixer or the like which is generally used for compound rubber production. White filler and chloropropyltrimethoxysilane The white filler containing silicon dioxide used in the present invention is a white rubber filler containing silicon dioxide as a constituent component, and specifically, dry process silica. , Wet process silica,
Examples thereof include synthetic silicate-based white carbon, talc, clay, calcined clay, and glass fiber. Wet silica and talc are preferable.

The compounding amount of these fillers is usually 5 parts with respect to 100 parts by weight of the ethylene / α-olefin copolymer rubber.
The proportion is from about 200 to about 200 parts by weight, preferably from 10 to 180 parts by weight, more preferably from 20 to 150 parts by weight.

Commercially available chloropropyltrimethoxysilane is used. The compounding amount of chloropropyltrimethoxysilane is 100 parts by weight of the above white filler.
5.0 × 10 ⁻³ mol to 3.0 × 10 ⁻¹ mol parts by weight, preferably 1.0 × 10 ⁻² mol to 2.5 × 10 ⁻¹ mol parts by weight, and more preferably 1.5 × 10 3. ^-2 mol ~ 2.0 x 1
0 ⁻¹ molar part.

Production of Rubber Laminate 1) Production of Compounded Rubber The chlorinated ethylene / α-olefin copolymer rubber (A) and ethylene / α-olefin copolymer rubber (B) of the present invention are generally used for rubber production. According to the formulation, compounding agents known per se according to the intended use of the vulcanized rubber and the performance based on the intended use, for example, vulcanizing agent, vulcanization aid, rubber reinforcing agent, pigment, filler, softening agent, metal activity Agent, screen
It is used by blending anti-challenge agent, hydrochloric acid absorbent, anti-aging agent, processing aid, foaming agent and the like. The method for producing the compounded rubber is not particularly limited. For example, a chlorinated ethylene / α-olefin copolymer rubber or ethylene / α-olefin copolymer rubber and additives such as a reinforcing agent, a filler, and a softening agent are Banbury-
After kneading at a temperature of about 80 ° C to 170 ° C for about 3 to 10 minutes using a non-open type kneading device such as a mixer or a kneader,
A vulcanizing agent and a vulcanization aid are additionally mixed using rolls such as open rolls, and the roll temperature is about 40 ° C to 80 ° C and the mixture is about 3 to 3 ° C.
The mixture is kneaded for 30 minutes and then dispensed to produce a ribbon-shaped or sheet-shaped rubber compound.

The adjustment of the vulcanization rate is extremely important for practical use in order to deal with various rubber processing steps. Therefore, a vulcanization aid is generally added. It is desirable to add a known vulcanization aid to the compounded rubber as needed. As the vulcanizing agent and the vulcanization aid (hereinafter referred to as vulcanization system),
Known vulcanization systems are used. Usually, sulfur vulcanization type, metal oxide vulcanization type, resin vulcanization type, quinoid vulcanization type, triazine vulcanization type, organic peroxide vulcanization type and the like can be exemplified. For chlorinated ethylene / α-olefin copolymer rubber, triazine vulcanization type and organic peroxide vulcanization type are preferable,
A sulfur vulcanization system is preferable for the α-olefin copolymer rubber.

The vulcanizing agent is 1 × 1 with respect to 100 parts by weight of rubber.
0 ^{−3 to} 7.0 × 10 ⁻² mol parts by weight, preferably 1.5 ×
10 ^{−3 to} 5.0 × 10 ⁻² mol parts by weight, more preferably 3
It is blended at a ratio of × 10 ^{-3 to} 4.0 × 10 ^-2 parts by weight.

When the compounding amount of the vulcanizing agent is smaller than the above range, a vulcanized product having suitable rubber elasticity cannot be obtained, and when the compounding amount is larger than the above range, the elongation is lowered and the composition is put to practical use. Tends to be difficult.

As the rubber reinforcing material, for example, SRF, G
PF, FEF, MAF, ISAF, SAF, FT, MT
Various carbon blacks such as, and finely divided silicic acid are appropriately used.

As the filler, for example, light calcium carbonate, heavy calcium carbonate, talc, clay and the like are used.

The amounts of these reinforcing materials and fillers to be blended are appropriately selected according to the desired product, but rubber 100
Normally 200 parts by weight or less, preferably 1 part by weight
It is compounded in an amount of 50 parts by weight or less.

As the softening agent, for example, process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, petroleum-based substances such as petrolatum, coal,
Colts such as pitch, castor oil,
Rapeseed oil, soybean oil, fatty oils such as coconut oil, tol oil, beeswax, carnauba wax, waxes such as lanolin, ricinoleic acid, palmitic acid, stearic acid, barium stearate, fatty acids such as calcium stearate, Or its metal salt, naphthenic acid or its metal soap, pine oil, rosin or its derivative, terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene, dioctyl phthalate, dioctyl adipate, dioctyl sebac -Ester plasticizers such as carbonates, carbonate plasticizers, other microcrystalline wax,
Examples include sub (factice), liquid polybutadiene, modified liquid polybutadiene, and liquid thiocol.

The blending amount of these softening agents is appropriately selected depending on the desired product, but is usually 100 parts by weight or less, preferably 70 parts by weight or less, relative to 100 parts by weight of rubber.

As the metal activator, magnesium oxide, zinc white, higher fatty acid zinc, red lead, litharge, calcium oxide, hydrotalcite and the like can be used.

These metal activators are usually used in an amount of 3 to 15 parts by weight, preferably 5 to 10 parts by weight, based on 100 parts by weight of rubber.
Used in the range of parts by weight.

As the anti-scorch agent, known anti-scorch agents can be used, and examples thereof include maleic anhydride, thioimide compounds, sulfenamide compounds and sulfonamide compounds. The above components are rubber 10
It is usually used in an amount of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, relative to 0 parts by weight.

For the chlorinated ethylene / α-olefin copolymer rubber, a hydrochloric acid absorbent is added if necessary. As the hydrochloric acid absorbent, oxides and organic acid salts of metals of Group 2A of the Periodic Table are generally used, and examples thereof include magnesium stearate, magnesia, calcium stearate, manaceite, hydrotalcite, epoxidized soybean oil, and epoxy-based hydrochloric acid absorbent. Can be exemplified. These hydrochloric acid absorbents are usually added in a proportion of 0.1 to 10 parts by weight with respect to 100 parts by weight of rubber.

Further, the compounded rubber of the present invention can improve the heat aging resistance by adding an antiaging agent, as in the case of a normal rubber. As the antiaging agent used in this case, known ones can be used, for example, aromatic secondary amine stabilizers such as phenylbutylamine, N, N'di-2-naphthyl-p-phenylenediamine, and dibutylhydroxy. Toluene, tetrakis [methylene (3,5-
Di-t-butyl-4-hydroxy) hydrocinname
To] methane and other phenolic stabilizers, bis [2-methyl-4- (3-n-alkylthiopropionyloxy)
Thioe such as -5-t-butylphenyl] sulfide
A ter-based stabilizer, a dithiocarbamate-based stabilizer such as nickel dibutyldithiocarbamate, and the like are used alone or in combination of two or more kinds. The amount of such an antiaging agent used is usually 0.1 to 5 relative to 100 parts by weight of rubber.
It is a part by weight, preferably 0.5 to 3 parts by weight.

As the processing aid, those used in the processing of usual rubbers can be used, and ricinoleic acid, stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate and the above-mentioned acids can be used. Examples thereof include higher fatty acids, salts thereof and esters thereof. These processing aids are usually used in an amount of up to about 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of rubber.

Examples of the foaming agent include inorganic foaming agents such as sodium hydrogen carbonate, ammonium carbonate and ammonium nitrite; N, N'-dimethyl-N, N'-dinitrosoterephthalamide, N, N'-dinitrosopentamethylene. Nitro compounds such as tetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexyl nitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonitrile hydrazide, toluenesulfonyl hydrazide, p, p '
-Sulfonyl hydrazide compounds such as oxybis (benzenesulfonyl hydrazide) and diphenyl sulfone-3,3'-disulfonyl hydrazide; calcium azide, 4,4'-diphenyl disulfonyl azide, p
-Azide compounds such as toluenesulfonyl azide are mentioned, in particular nitro compounds, azo compounds and azide compounds are preferably used.

These blowing agents are chlorinated ethylene / α-
The olefin copolymer rubber (A) or the ethylene / α-olefin copolymer rubber (B) may be blended in either one or both. The compounding amount is usually 0.3 to 30 parts by weight, preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the rubbers (A) to (B). This can generally form a foam having an apparent specific gravity of about 0.03 to 0.9.

Examples of the foaming aid which can be used together with the foaming agent include organic acids such as salicylic acid, phthalic acid and stearic acid, urea or its derivatives, and the like, which lowers the decomposition temperature of the foaming agent, promotes decomposition, and foams. Shows the function of equalizing the.

2) Production of Rubber Laminated Body The rubber laminated body according to the present invention comprises the above-mentioned chlorinated ethylene.
It is composed of a layer made of α-olefin copolymer rubber (A) and a layer made of ethylene / α-olefin copolymer rubber (B), and can be obtained by laminating both layers. Chlorinated ethylene / α-olefin copolymer rubber (A) of the present invention
The method for laminating the layer formed of the ethylene / α-olefin copolymer rubber (B) is not particularly limited, but the layer is manufactured as follows, for example. Chlorinated ethylene
α-olefin copolymer rubber (A) and ethylene / α-
Extruder, calendar for olefin copolymer rubber (B)
The sheet is preliminarily separately molded into a sheet shape, a tube shape or the like by using a molding machine or the like, and then a preformed body of the layer consisting of (A) and the layer consisting of (B) is calendered, A method of laminating using a compression molding machine or the like, in which either (A) or (B) is preformed in advance into a sheet shape, a tube shape, or the like,
Method of laminating while molding the other with an extrusion molding machine or calendar molding machine, multi-layer extrusion molding machine or multi-layer calender
A rubber laminated body is obtained by a method such as simultaneously laminating a layer composed of (A) and a layer composed of (B) using a molding machine. Subsequently or thereafter, the desired vulcanized rubber laminate can be obtained by vulcanizing in a hot air heating tank, a glass beads fluidized bed, a microwave heating tank, a salt bath heating tank, or a steam bath.

The interlaminar interfacial adhesion after vulcanization of the rubber laminate of the present invention is determined by the fact that the chlorinated ethylene / α-olefin copolymer rubber (A) in one layer contains a triazine compound and ethylene in the other layer. -When the α-olefin copolymer rubber (B) contains a filler containing silicon dioxide and chloropropyltrimethoxysilane, it is remarkably improved.

Although its function is not clear, a covalent bond is formed between the layer composed of the chlorinated ethylene / α-olefin copolymer rubber (A) and the layer composed of the ethylene / α-olefin copolymer rubber (B). It seems to be to do. In the present invention, the layer thickness of the chlorinated ethylene / α-olefin copolymer rubber (A) is 0.01 to 3 m.
m, and the thickness of the layer composed of the ethylene / α-olefin copolymer rubber (B) is preferably 1.0 to 10 mm.

[0043]

The rubber laminate according to the present invention comprises, as a vulcanized rubber laminate, a layer comprising chlorinated ethylene / α-olefin copolymer rubber (A) and ethylene / α-olefin copolymer rubber (B). Since the layers have excellent interlayer adhesion, they have excellent heat aging resistance, cold resistance, weather resistance, and oil resistance. Therefore, the rubber laminate of the present invention can be used in applications such as rubber parts for automobiles, industrial rubber products, civil engineering building materials, rubberized fabrics, and foamed rubber products.

[0044]

EXAMPLES The present invention will be described below with reference to examples. Physical property
The test method was as follows. Test method (1) Heat aging resistance According to JIS K1601, aging at 120 ° C for 70 hours
The tensile strength and elongation after the accelerated test were measured. (2) Cold resistance A German torsion test is performed according to ASTM D1053.
I asked for T5. (3) Oil resistance Assuming the conditions for wax removal, use a 5% aqueous suspension of kerosene.
85 ° C, 10 kg / cm ²20 cm away from the corner
Spraying for 10 seconds on the thin layer side of the two-layer sheet fixed at 40 degrees
The swelled state according to the following criteria: ◎-○-△-×
Visually determined. ⊚: No change, ○: Swelling a little Δ: Swelling obviously, ×: Swelling significantly (4) Weather resistance A two-layer sheet was subjected to an accelerated test using a xenon weather meter.
On the thin layer side, temperature 75 ℃, irradiation energy -0.35
w / m²Under the condition of 120-minute cycle (including 18-minute rainfall)
After 1000 hours, the appearance is ◎-○-△ according to the following criteria.
It was visually judged in the rank of -x. ◎: No change at all, ○: Little change in hue, no cracks △: Large change in hue, few cracks, ×: Remarkable hue
Change / Large crack generation (5) Adhesion between layers According to JISK6301, a peeling test was conducted at a temperature of 2
Contact in 1 inch at 5 ℃ and 70 ℃.
I asked for my strength. Example 1 4.3 L Banbury mixer (Kobe
It was kneaded for 5 minutes with a steel manufacturing company) and dumped out. Then,
Dumped out the kneaded product with 14 intio rolls
It was wrapped around (manufactured by Nippon Roll Co., Ltd.). At this time the roll surface
The temperature was 60 ° C. for the front roll and 70 ° C. for the rear roll. This
2 minutes after adding the compounding ingredients shown in Table 2 on the open roll of
After kneading, put out a sheet with a thickness of 3 mm and mix
-(Hereinafter referred to as C-1) was manufactured.

[0045]

[Table 1] ───────────────────────────── Ingredients by weight ────────────── ──────────────── Chlorinated ethylene / 1-butene copolymer rubber 1) 100.0 Stearic acid 3.0 Magnesia 2) 5.0 Talc 3) 120.0 Naphthene series Process oil 4) 35.0 Titanium white 5) 2.0 ───────────────────────────── 1) Ethylene / 1-butene (Molar ratio) 90/10 ML _{1 + 4} (121 ° C.) 50 Chlorine content 27 wt% 2) Brand name: Kyowamag 150 [Kyowa Kagaku] 3) Brand name: Mistronbeper talc [Japan Talc] 4) Brand name: Sun Sen 4240 [Japan Sun Oil] 5) Product Name: Titanium White R820 [Sakai Chemical]

[0046]

[Table 2] ───────────────────────────────────────────────────────────────────── ──────────────── Dibutylaminotriazinedithiol 2.0 Benzoic acid / piperidine salt 3.0 Benzoic acid / dicyclohexylamine salt 3.0 ──────── ─────────────────────

Next, the compounding agents shown in Table 3 were kneaded in a 4.3 L Banbury mixer and dumped out in the same procedure as in C-1. Then, the dumped-out kneaded material was wrapped around a 14-inch thiol roll, and the compounding agents shown in Table 4 were added and kneaded with this open roll, and then a sheet having a thickness of 3 mm was taken out to prepare a compounded rubber sheet ( Hereinafter referred to as E-1)
Was manufactured.

[0048]

[Table 3] ───────────────────────────── Ingredients by weight ────────────── ──────────────── Ethylene propylene rubber 1) 100.0 Stearic acid 2.0 Zinc white 2) 5.0 FEF carbon 3) 120.0 Naphthenic process oil 4 ) 60.0 ───────────────────────────── 1) Ethylene / Propylene (molar ratio): 72/28 ML _{1 + 4} (121 ° C): 70 Diene component: 5-ethylidene-2-norbornene Iodine value: 12 2) Trade name: Zinc Hua No. 1 [Sakai Chemicals] 3) Trade name: Cast SO [Tokai Carbon] 4) Product name: Sun Sen 4240 [Japan Sun Oil]

[0049]

[Table 4] ───────────────────────────── Ingredients by weight ────────────── ──────────────── Vulcanization aid CBS1) 0.5 〃 MBT2) 0.8 〃 TMTD3) 0.8 〃 DPTT4) 0.5 〃 TeEDC5) 0.5 Sulfur 1.0 ───────────────────────────── 1) Product name: Noxera-CZ [Ouchi Emerging] 2) Product name: 〃 M [Shinko Ouchi] 3) Brand name: 〃 TT [Shinko Ouchi] 4) Product name: TRA [Shinko Ouchi] 5) Product name: TL [Shinko Ouchi]

These compounded rubbers C-1 and E-1 were
The two sheets were supplied to two extruders attached to a two-layer die, and a two-layer laminated sheet was extrusion-molded. The extruder is manufactured by Nakata Zoki, the L / D is 12, and the extrusion temperature is 70.
C., the take-up speed was 3 m / min. This was continuously vulcanized for 10 minutes in a hot air heating tank set at 200 ° C.
The vulcanized two-layer laminated sheet has a thickness of 2 mm and is C-1.
The layer made of is 0.2 mm, the layer made of E-1 is 1.8 m
It was m. Using the obtained vulcanized rubber laminated sheet having a thickness of 2 mm, the heat aging test, cold resistance, oil resistance and weather resistance were examined according to the above measuring methods. The results of these measurements are shown in Table 9.

Example 2 The procedure of Example 1 was repeated except that the compounding agents shown in Table 5 were used instead of the compounding agents shown in Table 1, and the compounded rubber sheet (hereinafter, referred to as C- 2) was produced. Next, the same procedure as in Example 1 was carried out except that C-2 was used instead of C-1 in Example 1. The results of these measurements are shown in Table 9.

[0052]

[Table 5] ─────────────────────────────────────────────────────────────────────────────── ──────────────── Chlorinated ethylene / 1-butene copolymer rubber 1) 100.0 Stearic acid 3.0 Magnesia 2) 5.0 FEF carbon 3) 110. 0 Naphthenic process oil 4) 60.0 ───────────────────────────── 1) Ethylene / 1-butene (molar ratio) 90/10 ML _{1 + 4} (121 ° C) 50 Chlorine content 27 wt% 2) Product name: Kyowamag 150 [Kyowa Kagaku] 3) Product name: Sist SO [Tokai Carbon] 4) Product name: Sansen 4240 [ Japan Sun Oil]

Comparative Example 1 In Example 1, except that the compounding agent shown in Table 6 was used instead of the compounding agent shown in Table 1 and the compounding agent shown in Table 4 was used instead of the compounding agent shown in Table 2. Performed in the same manner as in Example 1,
A compounded rubber sheet (hereinafter referred to as E-2) was manufactured.
Next, in Example 1, it carried out like Example 1 except having used E-2 instead of C-1. The results of these measurements are shown in Table 9.

[0054]

[Table 6] ─────────────────────────────────────────────────────────────── ──────────────── Ethylene propylene rubber 1) 100.0 Stearic acid 2.0 Zinc white 2) 5.0 Talc 3) 120.0 Naphthenic process oil 4) 35. 0 Titanium white 5) 2.0 ───────────────────────────── 1) Ethylene / propylene (molar ratio): 72/28 ML _{1 + 4} (121 ° C.): 70 Diene component: 5-ethylidene 2-norbornene Iodine number: 12 2) Trade name: Zinc Hua No. 1 [Sakai Chemical Industry Co., Ltd.] 3) Trade name: Mistron Beper Talc [Japan Talc] 4) Product name: Sansen 4240 [Japan Sun Oil] 5) Product name: Titanium White R820 [Sakai Chemical]

Comparative Example 2 C-2 of Example 2 was used instead of E-1 in Example 1.
The same procedure as in Example 1 was carried out except that was used. The results of these measurements are shown in Table 9.

Comparative Example 3 The procedure of Example 1 was repeated except that C-1 was used instead of E-1. The results of these measurements are shown in Table 9.

Comparative Example 4 The procedure of Example 1 was repeated, except that E-1 was used instead of C-1. The results of these measurements are shown in Table 9.

Example 3 Example 1 was repeated except that the compounding agents shown in Table 7 were used instead of the compounding agents shown in Table 1.
A compounded rubber sheet (hereinafter referred to as E-3) was manufactured.
Next, in Example 1, it carried out like Example 1 except having used E-3 instead of E-1. The results of these measurements are shown in Table 9.

[0059]

[Table 7] ───────────────────────────── Ingredients by weight ────────────── ──────────────── Ethylene propylene rubber 1) 100.0 Stearic acid 2.0 Zinc white 2) 5.0 FEF carbon 3) 100.0 Naphthenic process oil 4 ) 60.0 Talc 5) 20.0 Chloropropyltrimethoxysilane 6) 0.5 ────────────────────────────── 1 ) Ethylene / propylene (molar ratio): 72/28 ML _{1 + 4} (121 ° C.): 70 Diene component: 5-ethylidene 2-norbornene Iodine value: 12 2) Trade name: Zinc Hua No. 1 [Sakai Chemistry] 3) Product name: Seast SO [Tokai Carbon] 4) Product name: Sun Sen 4240 [Japan Sun Oil] 5) Product name: Mistron Beer Talc [Japan Torque] 6) Product Name: Wakka - silane GF16S [Wakka -]

Example 4 Example 1 was repeated except that C-2 was used instead of C-1 and E-3 was used instead of E-1. The test results are shown in Table 5.

Example 5 The procedure of Example 1 was repeated except that the compounding agent shown in Table 8 was used in place of the compounding agent shown in Table 3, and the compounded rubber sheet (hereinafter referred to as E-4) was used. Referred to as). Next, Example 1 was repeated except that E-4 was used instead of E-1. Table 9 shows these measurement results.
Shown in.

[Table 8] ──────────────────────────────────────────────────────────────────────────── ──────────────── Ethylene propylene rubber 1) 100.0 Stearic acid 2.0 Zinc white 2) 5.0 FEF carbon 3) 60.0 Naphthenic process oil 4 ) 60.0 Silica 5) 40.0 Chloropropyltrimethoxysilane 6) 3.0 ────────────────────────────── 1 ) Ethylene / propylene (molar ratio): 72/28 ML _{1 + 4} (121 ° C.): 70 Diene component: 5-ethylidene 2-norbornene Iodine value: 12 2) Trade name: Zinc Hua No. 1 [Sakai Chemistry] 3) Product name: Seast SO [Tokai Carbon] 4) Product name: Sansen 4240 [Japan Sun Oil] 5) Product name: Nipsil VN3 [Japan Silica] 6) Product Name: Wacker Silane GF16S [Wacker]

[Table 9]

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location C08L 23/08 23/28 (72) Inventor Akemi Utsumi 3 Chikusaigan, Ichihara-shi, Chiba Mitsui Petrochemical Co., Ltd. Gaku Kogyo Co., Ltd.

Claims (5)

[Claims] 1. A chlorine content of 20-40% by weight,
Two-viscosity [ML _{1 + 4} (121 ° C.)] consisting of a chlorinated ethylene / α-olefin copolymer rubber (A) having a viscosity of ₁₀ to 190 and an ethylene / α-olefin copolymer rubber (B). And a chlorinated ethylene.
Rubber laminate in which the α-olefin copolymer rubber (A) contains a triazine compound 2. The chlorinated ethylene / α-olefin copolymer rubber (A) contains a triazine compound as chlorinated ethylene / α.
3. Per 100 parts by weight of olefin copolymer rubber (A).
The rubber laminate according to claim 1, containing 0 × 10 ⁻⁴ mol to 3.0 × 10 ⁻² mol parts by weight. 3. The rubber laminate according to claim 1, wherein the triazine compound is triazine thiol. 4. The ethylene / α-olefin copolymer rubber (B) contains a filler containing silicon dioxide and chloropropyltrimethoxysilane.
The rubber laminate according to 5. The vulcanized rubber laminate according to claim 1, wherein the rubber laminate is vulcanized.