JPH04202237A - Vulcanized rubber molding and preparation thereof - Google Patents

Abstract

PURPOSE:To obtain the title molding excellent in surface flatness, dimensional stability, and sealing properties by vulcanizing a vulcanizable molding which comprises an ethylene-alpha-olefin copolymer and is coated with a specific coating soln. CONSTITUTION:A vulcanizable molding which comprises an ethylene-alpha-olefin copolymer (e.g. ethylene-propylene-diene terpolymer) and is coated with a coating soln. contg. at least one xanthate vulcanization accelerator of the formula (wherein R is 1-30C alkyl; and M is a metal or ammonium) is vulcanized.

Description

DETAILED DESCRIPTION OF THE INVENTION Technical Field of the Invention The present invention relates to a vulcanized rubber molded article (including not only a vulcanized rubber non-foamed article but also a vulcanized rubber foamed article) and a method for producing the same. Ethylene-α with excellent smoothness
- It relates to a vulcanized rubber molded article made of olefin copolymer rubber and a method for producing the same, particularly a vulcanized rubber foam and a method for producing the same.

TECHNICAL BACKGROUND OF THE INVENTION Vulcanized rubber foams are widely used in cushioning materials, sealing materials, soundproofing materials, electrical insulation materials, and other applications. In recent years, there has been a desire for a vulcanized rubber foam that has even better surface smoothness than conventional vulcanized rubber foams from the viewpoint of sealability or fashionability.

By the way, in order to obtain a vulcanized rubber foam with excellent surface smoothness, methods of adjusting the vulcanization rate and foaming rate, as well as methods of adjusting the heat transfer rate by changing the heating method, have been studied. Ta.

However, all of the vulcanized rubber foams obtained using the above method have insufficient surface smoothness and surface roughness [JI using Surf Rubber 200B manufactured by Tokyo Seimitsu Co., Ltd.].
The limit value of measurement according to SB-0601 is 10μ
It was m.

Therefore, the present inventors conducted extensive research to obtain a vulcanized rubber foam with excellent surface smoothness, and developed a tubular vulcanizable foam made of ethylene/α-olefin copolymer rubber extruded from an extruder. The foamable molded article was continuously dipped in an isopropyl alcohol suspension of a xanthate-based vulcanizing agent, and then introduced into a hot air vulcanization tank for vulcanization and foaming. The present inventors have discovered that a vulcanized rubber foam with excellent surface smoothness and a surface roughness of .

In recent years, sealing foams have become larger and more complex in shape, and high shape retention is required, so the method for producing vulcanized rubber foams as described above is extremely useful industrially.

In addition, the present inventors have found that if the above method is adopted for non-expandable vulcanizable rubber molded products, vulcanized rubber molded products with excellent surface smoothness and shape retention stability can be obtained. I discovered that.

Purpose of the Invention The present invention aims to solve the problems associated with the prior art as described above, and provides a vulcanized rubber molded article with excellent surface smoothness and shape retention stability, and a method for producing the same, particularly vulcanized rubber molded articles with excellent surface smoothness and shape retention stability. The object of the present invention is to provide a sulfur rubber foam and a method for producing the same.

Summary of the Invention The first vulcanized rubber molded article according to the present invention contains at least one xanthate-based vulcanization accelerator represented by the following chemical formula.
It is characterized in that it is made by vulcanizing a vulcanizable molded article made of ethylene-α-olefin copolymer rubber that has been surface-treated with a coating liquid containing various types of rubber.

In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, and M is a metal or ammonium.

Further, the first method for producing a vulcanized rubber molded body according to the present invention includes adding a xanthate salt system represented by the above chemical formula to the surface of a vulcanizable molded body made of ethylene/α-olefin copolymer rubber. It is characterized in that the molded body is vulcanized by applying a coating liquid containing at least one type of vulcanization accelerator.

The second vulcanized rubber molded article according to the present invention contains at least one xanthate-based vulcanization accelerator represented by the above chemical formula.
It is characterized by being formed by vulcanizing and foaming a vulcanizable and foamable molded product made of ethylene/α-olefin copolymer rubber, which has been surface-treated with a coating liquid containing various types of rubber.

In addition, the second method for producing a vulcanized rubber molded article according to the present invention includes applying a compound represented by the above chemical formula to the surface of a vulcanizable and foamable molded article made of ethylene-α-olefin copolymer rubber. The method is characterized in that the molded article is vulcanized and foamed by applying a coating liquid containing at least one type of xanthate-based vulcanization accelerator.

DETAILED DESCRIPTION OF THE INVENTION The vulcanized rubber molded article and the method for producing the same according to the present invention will be specifically described below.

The first vulcanized rubber molded article according to the present invention contains at least one xanthate-based vulcanization accelerator represented by the following chemical formula.
This is a non-foamed molded product obtained by vulcanizing a vulcanizable molded product made of ethylene/α-olefin copolymer rubber that has been surface-treated with a coating liquid containing various types.

[R-0-C-3-co,,M'' In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, and M is a metal or ammonium.

Further, the second vulcanized rubber molded article according to the present invention has an ethylene-α
- It is a foamed product obtained by vulcanizing and foaming a vulcanizable and foamable molded product made of olefin copolymer rubber.

Ethylene/α-olefin copolymer rubber The ethylene/α-olefin copolymer rubber used in the present invention is composed of ethylene and an α-olefin having 3 or more carbon atoms, or ethylene and an α-olefin having 3 or more carbon atoms. It is a binary, ternary, quaternary or higher copolymer consisting of an olefin and a non-conjugated polyene.

The α-olefin constituting the above-mentioned ethylene/α-olefin copolymer rubber is usually, specifically, propylene,
α-olefins such as 1-butene, ■-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, and l-decene are used alone or in combination. .

In the present invention, propylene and 1-butene are preferably used.

The molar ratio of ethylene and α-olefin constituting the above ethylene/α-olefin copolymer rubber (ethylene/α-olefin
-olefin) is 50150 to 9515, preferably 60/40 to 93/7, more preferably 70/30 to
It is 91/9.

Specifically, the non-conjugated polyene constituting the ethylene/α-olefin copolymer rubber includes 1,4-hexadiene, 1,6-octadiene, 5-methyl-1,4
- Chain non-conjugated diene compounds such as hexadiene; cyclohexadiene, dicyclopentadiene, methyltetrahydroindene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropylidene-2
- Cyclic non-conjugated diene compounds such as norbornene: 2.8-convex pyridene-5-norbornene, 2-
Bropenyl-2,2-norbornadiene, I, 8.7-
Examples include triene compounds such as octatriene, and these compounds may be used alone or in combination.

In the present invention, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, and 1,4-hexadiene are particularly preferred, and these compounds may be used alone or in combination.

The content of these non-conjugated dienes is up to 5 in terms of iodine value.
0, preferably a maximum of 40. More preferably, it is at most 30, and in terms of mol%, it is at most 10 mol%, preferably at most 7 mol%, and even more preferably at most 5 mol%.

Coating Solution The coating solution used in the present invention is a solution or suspension containing at least one xanthate-based vulcanization accelerator represented by the following chemical formula.

[R-0-C-8-], M'' In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, and M is a metal or ammonium.

Specific examples of the xanthate-based vulcanization accelerator represented by the above chemical formula include sodium isopropyl xanthate, zinc isopropyl xanthate, zinc ethyl xanthate, zinc butyl xanthate, and the like. These compounds may be used alone or in combination of two or more.

In addition to the xanthate-based vulcanization accelerator mentioned above, this coating solution also contains other vulcanization accelerators, such as amine-based vulcanization accelerators, thiazole-based vulcanization accelerators, and thiuram-based vulcanization accelerators. One or more types of accelerators and dithiocarbamic acid vulcanization accelerators can be included.

Furthermore, if necessary, in addition to the above-mentioned vulcanization accelerator, additives such as a vulcanizing agent, a vulcanizing aid, and an anti-aging agent may be added to this coating solution within a range that does not impair the purpose of the present invention. can be included.

The solvent used for this coating solution is a solvent that can dissolve the xanthate-based vulcanization accelerator, and a solvent that cannot dissolve the xanthate-based vulcanization accelerator, but can be stirred with a mixer etc. Examples include solvents that can be used in a suspended state. In the present invention, compounds such as the above-mentioned xanthate-based vulcanization accelerators may be dissolved by adding various surfactants to the solvent.

The concentration of the xanthate-based vulcanization accelerator in the above-mentioned coating liquid is preferably 0.1% by weight or more, and more preferably in the range of 1 to 10% by weight.

When this concentration is less than 0.1% by weight, in order to fully achieve the effects of the present invention, it is necessary to It is necessary to increase the number of times the coating liquid is applied to the vulcanizable and foamable molded body made of the composite rubber, and therefore production efficiency deteriorates.

Examples of surface treatment methods using coating liquids as described above include methods such as coating with a brush and dipping.
In the case of continuous coating, a surface treatment method using dipping is preferred.

In addition, the amount of coating liquid applied is usually 0.00 in terms of solid content.
1 to 50 g/rri, preferably 0.1 to 5 g/rri.

The vulcanizable molded product or the vulcanizable and foamable molded product made of the above ethylene/α-olefin copolymer rubber is subjected to surface treatment with the above coating liquid before vulcanization or vulcanization and foaming. By applying this, a molded article with excellent surface smoothness can be obtained. In the present invention, a foam having a surface roughness of 10 μm or less, which has not been obtained conventionally, can be obtained.

The vulcanized rubber molded article according to the present invention is a vulcanizable molded article or a vulcanizable and foamable molded article made of an ethylene/α-olefin copolymer rubber as described above, and is coated with a coating liquid as described above. It is obtained by surface treatment with and then vulcanization or vulcanization foaming.

In addition to the ethylene/α-olefin copolymer rubber, which is an essential component, the rubber compound constituting the above-mentioned vulcanizable molded product is made of rubber compounded according to the processability and required performance in manufacturing the molded product. , conventionally known compounding agents such as vulcanizing agents, vulcanization aids, rubber reinforcing agents, fillers, softeners, metal activators,
Compounds with oxymethylene structure, scorch inhibitors,
Anti-aging agents, processing aids, etc. can be added.

In addition to the above-mentioned essential components, the rubber compound constituting the above-mentioned vulcanizable and foamable molded product may include a blowing agent,
In addition to the foaming aid, conventionally known compounding agents such as those mentioned above can be blended.

Vulcanizing agents used in rubber compounds such as those described above include sulfur, sulfur compounds, organic peroxides, and reactive phenolic resins.

Specific examples of the above sulfur include powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur.

Specific examples of the above-mentioned sulfur compounds include sulfur chloride, sulfur dichloride, and polymer polysulfides. Examples of sulfur compounds that release active sulfur at the vulcanization temperature and participate in vulcanization include morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, and the like.

In the present invention, the above sulfur and sulfur compounds are usually 0.05 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the ethylene/α-olefin copolymer rubber. used at a rate of

Specifically, the above-mentioned organic peroxides include dicumyl peroxide, dije+t-butyl peroxide, 2.
5-dimethyl-2,5-di(le r l-butylperoxy)hexane, 2,5-dimethyl-2,5-di(1'e+1-butylperoxy)hexane-3,1,
3-bis(lert-butylperoxyisopropyl)
Benzene, 1,1-bis(ler)-butylperoxy)-3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis(ter l-butylperoxy)valerate, benzoyl peroxide, p-
chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 1e11-butyl peroxybenzoate, 1eN-butyl perbenzony), jerl
-Butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, l! +1
-Butylcumyl peroxide, etc. can be mentioned.

Among these, it ranks 2.5 in terms of odor and scorch stability.
-dimethyl-2,5-di(+e+t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(le
+ 1-butylperoxy)hexyne-3,1,3-bis(l e r 1-butylperoxyisopropyl)
benzene, 1,1-bis(tcrt-butylperoxy)-3,3,5-trimethylcyclohexane, and n
-butyl-4,4-bis(+ et l-butylperoxy)valerate is preferred, and 1,3-bis(jerl-butylperoxyisopropyl)benzene is most preferred.

In the present invention, the above organic peroxide is ethylene,
0 parts by weight of α-olefin copolymer rubber
．． It is used in a proportion of 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight.

Specific examples of the above-mentioned reactive phenol resins include alkylphenol-formaldehyde resins, octylphenol-formaldehyde resins, and the like.

In the present invention, the above-mentioned reactive phenol resin is used in an amount of 0.5 to 30 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the ethylene/α-olefin copolymer rubber.

Specific examples of the blowing agent include inorganic blowing agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, ammonium nitrite, N,N'-dimethyl-N, N'-dinitrosoterephthalamide, N
, N'-dinitrosopentamethylenetetramine and other nitroso compounds; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate; benzenesulfonylhydrazide, toluenesulfonyl Hydrazide, p,p'-oxyhis(benzenesulfonylhydrazide), diphenylsulfone-3,3'
- Sulfonyl hydrazide compounds such as disulfonyl hydrazide; azide compounds such as calcium azide, 4.4'-diphenyldisulfonyl azide, p-toluenesulfonyl azide, etc., and nitroso compounds, azo compounds and azide compounds are particularly preferably used. .

The above blowing agent is used in an amount of 1.0 x 10-3 mol-3 per 100 g of ethylene/α-olefin copolymer rubber.
,0X10'mol, preferably from 2.0X10'mol to 2
．． It is blended in a proportion of 0x10-' moles. In this case, a foam having an apparent specific gravity of approximately 0.03 to 0.7 is generally obtained.

Specific examples of foaming aids that can be used together with the foaming agent include organic acids such as salicylic acid, phthalic acid, and stearic acid, or urea or its derivatives. The foaming aid has functions such as lowering the decomposition temperature of the foaming agent, accelerating decomposition, and making bubbles uniform.

Specifically, the rubber reinforcing agent is SRF.

GPE, FEF, MAFXHAF, I SAF.

Various carbon blacks such as SAF, FT, and MT, finely powdered silicic acid, and the like are used as appropriate.

Specifically, light calcium carbonate, heavy calcium carbonate, talc, clay, etc. are used as the filler.

These reinforcing agents and fillers are both ethylene α
- The amount of the olefin copolymer rubber is usually 200 parts by weight or less, preferably 150 parts by weight or less, based on 100 parts by weight of the rubber.

Examples of softeners include process oils, lubricating oils, paraffin, liquid paraffin, petroleum asphalt, petroleum-based substances such as petrolatum, coal tars such as coal tar and coal tar pitch, castor oil, linseed oil, Fatty oils such as rapeseed oil and coconut oil, tall oil, sub, beeswax,
Waxes such as carnauba wax and lanolin, ricinoleic acid,
Fatty acids or their metal salts such as palmitic acid, barium stearate, calcium stearate, synthetic polymers such as petroleum resins, atactic polypropylene, coumaron indene resins, ester plasticizers such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate, etc. ,
Other microcrystalline wax, sub (factice), liquid polybutadiene, modified liquid polybutadiene,
Examples include liquid thiocol.

The above-mentioned softeners are usually blended in an amount of 100 parts by weight or less, preferably 70 parts by weight or less, per 100 parts by weight of the ethylene/α-olefin copolymer rubber.

Specific examples of the metal activator include magnesium oxide, higher fatty acid zinc, red lead, litharge, and calcium oxide. The metal activator as described above is 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 the ethylene/α-olefin copolymer rubber.

Furthermore, in order to cope with various rubber processing steps, it is desirable to add a compound having an oxyethylene structure and a scorch inhibitor.

Specific examples of the compound having an oxyethylene structure include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, and polypropylene glycol.

The compound having an oxyethylene structure as described above is usually used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of ethylene/α-olefin copolymer rubber. .

As the scorch inhibitor, a known scorch inhibitor can be used, and specific examples include maleic anhydride, thioimide compounds, sulfenamide compounds, and sulfonamide compounds.

The above scorch inhibitor is usually used in an amount of 0.2 parts by weight per 100 parts by weight of ethylene/α-olefin copolymer rubber.
It is used in an amount of ˜5 parts by weight, preferably 0.3 to 3 parts by weight.

Furthermore, if an anti-aging agent is used, it is possible to extend the material life of the molded article of the present invention, and specific examples of such an anti-aging agent include phenylnaphthylamine, N
, N'-di-2-naphthyl-p-phenylenediamine, etc., dibutylhydroxytoluene, tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate] Phenolic stabilizers such as methane, bis[2-methyl-4-(3-n-
A thioether stabilizer such as alkylthiopropionyloxy)-5-1-butylphenyl cosulfide, a dithiocarbamate stabilizer such as nickel dibutyldithiocarbamate, etc. may be blended alone or in combination of two or more.

The above anti-aging agent is usually used in an amount of 0.1 to 5 parts by weight per 100 parts by weight of ethylene/α-olefin copolymer rubber.
It is used in an amount of 0.5 to 3 parts by weight, preferably 0.5 to 3 parts by weight.

As processing aids, compounds commonly used in rubber processing can be used, specifically ricinoleic acid,
Examples include higher fatty acids, salts thereof, and esters thereof, such as stearic acid, palmitic acid, lauric acid, barium stearate, calcium stearate, zinc stearate, and esters of the above acids.

The above-mentioned processing aids are generally used in an amount of about 10 parts by weight or less, preferably about 1 to 5 parts by weight, per 100 parts by weight of the ethylene/α-olefin copolymer rubber.

Furthermore, other types of rubber such as ethylene-propylene rubber, butyl rubber, SBR, etc. may be blended within a range that does not impair the performance of the rubber compound.

Next, a rubber compound as described above is prepared, for example, in the following manner.

That is, ethylene/α-olefin copolymer rubber and compounding agents such as reinforcing agents, fillers, and softeners are heated at approximately 80 to 170°C using a mixer such as a Banbury mixer.
After kneading for about 3 to IC minutes at a temperature of ,
Next, the mixture is kneaded and separated at a roll temperature of about 40 to 80° C. for about 5 to 30 minutes to prepare a ribbon-like or sheet-like rubber compound.

In addition, by directly feeding the ethylene/α-olefin copolymer rubber and compounding agents to an extruder heated to about 80 to 100°C and allowing a residence time of about 0.5 to 5 minutes, pelletized rubber can be produced. Formulations can also be prepared.

The rubber compound prepared in this way is generally molded using an extruder, and the molded product is surface-treated with the above-mentioned coating liquid by a method such as dipping. This molded body is heated under no pressure using a wave heating device or the like to vulcanize or vulcanize and foam.

The heating temperature in this case is 150 to 270°C, and vulcanization,
The time required for foaming is 1 to 30 minutes.

The vulcanized rubber non-foamed material obtained as above has excellent surface smoothness compared to conventional vulcanized rubber non-foamed material, and its surface roughness (Its B-0601) is 5 μm or less. It is.

In addition, the vulcanized rubber foam obtained as described above has superior surface smoothness compared to conventional vulcanized rubber foams, and its surface roughness (Its B-0601) is 10 μm.
It is as follows. In this way, a vulcanized rubber foam with excellent surface smoothness can be obtained because the coating liquid for surface treatment is vulcanizable and foamable, consisting of ethylene/α-olefin copolymer rubber. The xanthate compound contained in the coating liquid penetrates the body surface and acts as a strong vulcanization accelerator, forming a so-called skin layer, and then the entire vulcanizable and foamable molded article as described above is cured. It is presumed that this is due to the occurrence of vulcanization foaming.

In addition, in the present invention, before vulcanization and foaming occur inside the vulcanizable and foamable molded product, a crosslinking reaction occurs on the surface of the molded product to form a skin layer. Excellent shape retention stability of molded products. The same can be said of the vulcanized rubber non-foamed material obtained as described above.

Effects of the Invention The first vulcanized rubber molded article according to the present invention, that is, the vulcanized rubber non-foamed article, is obtained by vulcanizing a vulcanizable molded article made of a specific synthetic rubber whose surface has been treated with a specific coating liquid. Because of this, it has excellent surface smoothness, shape retention stability, and excellent sealing properties. The vulcanized rubber non-foamed material of the present invention has a surface roughness, which is an index of surface smoothness, of 5 μm or less.

In addition, the second vulcanized rubber molded product according to the present invention, that is, the vulcanized rubber foam, is a vulcanizable and foamable molded product made of a specific synthetic rubber that has been surface-treated with a specific coating liquid. Since it is made by foaming sulfur, it has excellent surface smoothness, shape retention stability, and excellent sealing properties. The vulcanized rubber foam of the present invention has a surface roughness, which is an index of surface smoothness, of 10 μm or less.

According to the method for manufacturing a first vulcanized rubber molded body according to the present invention, a first vulcanized rubber molded body according to the present invention having the above effects can be obtained.

Moreover, according to the method for producing the second vulcanized rubber molded body according to the present invention, the second vulcanized rubber molded body according to the present invention having the above effects can be obtained.

EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

In addition, the testing methods for physical properties in Examples and Comparative Examples are as follows.

[Test Method] (1) Apparent Specific Gravity The apparent specific gravity was measured by the substitution method using an automatic hydrometer manufactured by Toyo Seiki Seisakusho Co., Ltd.

(2) Surface roughness The surface roughness is determined according to the method of JIS B-0601 (
The measurement was performed using Surf Rubber 200B manufactured by Tokyo Seimitsu Co., Ltd.

Example 1 A foam was produced according to the following procedure and subjected to the above test.

First, the formulations shown in Table 1 below were kneaded for 5 minutes in a 4.31 Banbury mixer [■ Kobe Steel Shinsei Kogyo.

Table 1 (Blends) 1) Ethylene Propylene Genterpolymer (EF
T); Manufactured by Mitsui Petrochemical Industries ■, Mooney viscosity ML
(100°C) 90, iodine value 22, ethylene content 68 mol% 2) Manufactured by Asahi Carbon ■, product number #50HG3) Manufactured by Idemitsu Kosan ■, trade name Diana Process Oil PW-380 4) Weight average molecular weight (Mw ): 4. OH, manufactured by Wako Tsumugi Co., Ltd. 5) Calcium oxide; manufactured by Benjo Lime Industry ■, product name VH2
Next, dump out the kneaded mixture around a 14-inch open roll (manufactured by Nippon Roll Co., Ltd.) heated to 50°C, and mix the ingredients shown in Table 2 below on the open roll. Added.

Table 2 1) 2-Mercaptobenzothiazole (MBT); manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusela-2) Zinc dibutyldithiocarbamate (2nBDC); manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusela 813) Tellurium diethyldithiocarbamate (TeEDC) ; Manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusera TTTE 4) 2-mercaptoimidacillin (EU), manufactured by Sanshin Kagaku Kogyo ■, trade name Suncella 22-05) Manufactured by Tsurumi Chemical Kogyo ■, trade name Kinka Fine powder sulfur 6) p
, p'-oxybis(benzenesulfonylhydrazide) (OBSH), Uniroyal (Uni'
Product name: Celogen OT manufactured by o7a l) Co., Ltd. After kneading the formulation shown in Table 1 and the formulation shown in Table 2 for 5 minutes as described above, the resulting mixture had a thickness of about 3 mm.

The compounded rubber was cut into a ribbon shape with a width of approximately 50 openings.

Next, the compounded rubber was fed to a 60 tnφ rubber extruder (manufactured by Chunichi Zoki Co., Ltd., L/D = 16, set temperature: die/cylinder (front)/cylinder (rear) = 80°C, 770°C/60°C). A tubular molding was extruded.

Next, this tubular molded product was continuously soaked in an isopropyl alcohol solution containing 10% by weight of zinc isopropyl xanthate (manufactured by Irinai Shinko Kagaku Kogyo ■, trade name Tsukusera XIX) (hereinafter referred to as "treatment liquid A"). After dipping into the hot air vulcanization tank, 2
Vulcanization and foaming were performed in an atmosphere of 20° C. for 5 minutes to obtain a tubular foam.

Table 3 shows the physical properties of the obtained foam.

Example 2 In Example 1, in place of the treatment solution A of Example 1, an isopropyl alcohol solution containing 10% by weight of zinc dibutylxanthate [manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusela 2BX] (hereinafter referred to as "treatment solution") was used. A foam was obtained in the same manner as in Example 1, except for using "Liquid B"), and a physical property test was conducted.

The results are shown in Table 3.

Example 3 In Example 1, in place of the treatment solution A of Example 1, an isopropyl alcohol solution containing 0.1% by weight of zinc dibutylxanthate [manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusela zBX] (hereinafter referred to as (referred to as “processing liquid C”)
A foam was obtained in the same manner as in Example 1, except that a foam was used, and a physical property test was conducted.

The results are shown in Table 3.

Example 4 In Example 1, a p-xylene solution (hereinafter referred to as " A foam was obtained in the same manner as in Example 1, except that a treatment liquid (referred to as "Treatment Liquid D") was used, and physical property tests were conducted.

The results are shown in Table 3.

Example 5 In Example 1, in place of the treatment solution A of Example 1, a 5% aqueous solution of dimethyl sulfoxide containing 10% by weight of zinc dibutylxanthate [manufactured by Iriuchi Shinko Kagaku Kogyo ■, trade name Tsukusela 28X] was used. A foam was obtained in the same manner as in Example 1, except that a foam (hereinafter referred to as "treatment liquid E") was used, and physical property tests were conducted.

The results are shown in Table 3.

Comparative Example 1 A foam was obtained in the same manner as in Example 1 except that dipping was omitted, and physical property tests were conducted.

The results are shown in Table 3.

Comparative Example 2 A foam was obtained in the same manner as in Example 1, except that an isopropyl alcohol solution (hereinafter referred to as "treatment liquid F") was used instead of treatment liquid A in Example 1. , physical property tests were conducted.

The results are shown in Table 3.

Example 6 A non-foamed molded product (hereinafter referred to as non-foamed product) was obtained in the same manner as in Example 1, except that the blowing agent QBSH in Table 2 was not used, and a physical property test was conducted. .

The results are shown in Table 4.

Example 7 A non-foamed body was obtained in the same manner as in Example 2, except that the blowing agent 0BSH in Table 2 was not used.
Physical property tests were conducted.

The results are shown in Table 4.

Comparative Example 3 A non-foamed body was obtained in the same manner as in Comparative Example 1, except that the blowing agent 0BS)i in Table 2 was not used, and a physical property test was conducted.

The results are shown in Table 4.

Comparative Example 4 A non-foamed body was obtained in the same manner as in Comparative Example 2, except that the blowing agent 0BSH in Table 2 was not used.
Physical property tests were conducted.

The results are shown in Table 4.

Table 4 (Vulcanized rubber non-foamed material)

Claims (6)

[Claims] (1) Vulcanize a vulcanizable molded article made of ethylene/α-olefin copolymer rubber that has been surface-treated with a coating liquid containing at least one xanthate-based vulcanization accelerator represented by the chemical formula below. Vulcanized rubber molded product characterized by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, and M is a metal or ammonium. be). (2) The vulcanized rubber molded article according to claim 1, wherein the surface roughness of the vulcanized rubber molded article is 5 μm or less. (3) A coating liquid containing at least one type of xanthate-based vulcanization accelerator represented by the chemical formula below is applied to the surface of a vulcanizable molded product made of ethylene/α-olefin copolymer rubber. A method for manufacturing a vulcanized rubber molded body characterized by vulcanizing the molded body; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, M is a metal, ammonium). (4) Vulcanizable and foamable molding made of ethylene/α-olefin copolymer rubber whose surface has been treated with a coating liquid containing at least one xanthate vulcanization accelerator represented by the chemical formula below. Vulcanized rubber molded product characterized by being formed by vulcanizing and foaming the body; ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above chemical formula, R is an alkyl group having 1 to 30 carbon atoms, and M is a metal, ammonium). (5) The vulcanized rubber molded article according to claim 4, wherein the vulcanized rubber molded article has a surface roughness of 10 μm or less. (6) A coating liquid containing at least one xanthate-based vulcanization accelerator represented by the chemical formula below is applied to the surface of a vulcanizable and foamable molded product made of ethylene/α-olefin copolymer rubber. A method for producing a vulcanized rubber molded body, which is characterized by coating and vulcanizing and foaming the molded body; an alkyl group, M is a metal, ammonium).