JPH03247636A - Dithiocarbamate compound and copolymer and rubber composition using same compound - Google Patents

Abstract

PURPOSE:To obtain dithiocarbamate compound useful as a deterioration inhibitor of a body panel or a bumper part material, etc., capable of imparting excellent weatherability to rubbery elastomer. CONSTITUTION:(A) 0.1-5wt.% dithiocarbamate compound expressed by the formula (R<1> and R<2> are H or 1-4C alkyl; R<3> is 1-3C alkylene) is copolymerized with (B) 5-80wt.%, preferably 10-80wt.% conjugated diene compound (e.g. butadiene or isoprene) and (C) 0-90wt.% another compound (e.g. vinyl cyanide compound or alpha, beta unsaturated carboxylic acid ester) to afford the aimed copolymer having Mooney viscosity: ML1+4(100 deg.C)=10-150. Otherwise, 100 pts.wt. a rubbery polymer (e.g. natural rubber or styrene-butadiene copolymer rubber) is mixed with 0.1-10 pts.wt. the component A to afford the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a dithiocarbamate compound, a copolymer using the same, and a rubber composition, and more specifically, a novel compound suitable for industrial materials with excellent weather resistance. The present invention relates to a dithiocarbamate compound, a copolymer using the same, and a rubber composition.

[Conventional technology]

In general, rubber-like elastic materials, especially those with unsaturated bonds in their molecular chains, undergo deterioration phenomena such as softening or hardening when exposed to the effects of ozone, oxygen, heat, light, etc., resulting in deterioration of the rubber properties. This results in a significant decrease, which often poses a problem in practice.

In order to prevent such deterioration, various anti-aging agents such as phenolic and amine-based anti-aging agents have been blended into rubber, and this has been shown to be quite effective in relatively moderate temperature environments.

However, recently, the environment in which products with rubber-like elasticity are used has become even more severe, and especially when used outdoors, greater weather resistance than before is required, and conventional anti-aging agents cannot meet these harsh conditions. Under the conditions of use, it has become impossible to prevent rubber products from deteriorating. Increasing the amount of anti-aging agent creates the problem of migration of the anti-aging agent to the surface of the product under the environment of use.

Therefore, there is a demand for an anti-aging agent that can maintain various physical properties at a high level even when used outdoors at high temperatures, and for a rubber-like elastic body that has excellent weather resistance.

[Problem to be solved by the invention]

An object of the present invention is to provide a dithiocarbamate compound which can solve the problems of the prior art described above, which can impart excellent weather resistance to a rubber-like elastic body even under high temperatures, and which does not migrate to the product surface. An object of the present invention is to provide a copolymer and a rubber composition using the same.

[Means to solve the problem]

In view of the above-mentioned problems, the present inventors have conducted extensive studies and have found that the present invention can be achieved by copolymerizing a specific compound or incorporating it in an appropriate amount in a rubber-like elastic body, and have arrived at the present invention.

That is, the first aspect of the present invention is -a formula (1) (wherein R1
and R2 are the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, and R3 is an alkylene group having 1 to 3 carbon atoms.

The second aspect of the present invention is to combine the dithiocarbamate compound (A) represented by the above formula (I), the conjugated diene compound (B), and another compound (C) copolymerizable with these into (A)
, 0.1 each for the total amount of (B) and (C)
-5% by weight, 5-80% by weight and 0-90% by weight of a copolymer obtained by polymerization, the copolymer having a Mooney viscosity MLI-4 (100°C) of 10-150.
It relates to a copolymer that is

The third aspect of the present invention is 100 parts by weight of a rubbery polymer and the -
Formula (I) dithiocarbamate compound (^) 0.1~
10 parts by weight of the rubber composition.

The dithiocarbamate compound of the present invention (hereinafter simply referred to as "compound (A)") has the formula (T) (wherein R'
and R2 are the same or different and are represented by a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably a hydrogen atom, and R3 is an alkylene group having 1 to 3 carbon atoms, preferably a methylene group), bis( After reacting dialkylene amine and carbon disulfide in equimolar amounts, 0.5 mole of nickel sulfate is added dropwise to react sequentially, and the crystals are collected by filtration and dried under reduced pressure. It can be obtained by

Specific examples of the compound (A) include the following compounds.

The compound (A) of the present invention can be copolymerized with other copolymerizable monomers to form a copolymer.

The copolymer of the present invention is obtained by polymerizing the compound (A), the conjugated diene compound (B), and another compound (C) copolymerizable with these.

The content of the above compound (A) in the copolymer is 0.1 to 5% by weight. If this amount is less than 0.1% by weight, the resulting copolymer will have poor weather resistance, and if it exceeds 5% by weight, the polymerization reaction will be inhibited, making it difficult to obtain a rubbery copolymer.

The above conjugated diene compound (B) is represented by general formula (II) (in the formula, R4, R5 and R& are the same or different and mean hydrogen or an alkyl group), and specific examples thereof include butadiene, isoprene, 1.3-pentagene,
Examples include 2,3-dimethylbutadiene, piperylene, and 1,3-hexadiene. Among these, butadiene and isoprene are particularly preferred.

The content of the conjugated diene compound (B) in the copolymer is 5 to 8
0% by weight, preferably 10-80% by weight. If this amount is less than 5% by weight, the processability of the resulting copolymer will deteriorate, and if it exceeds 80% by weight, the mechanical strength of the copolymer will decrease.

The other copolymerizable compounds (C) include vinyl cyanide compound (a), α, β unsaturated carboxylic acid ester (b), crosslinkable monomer (C), and various monomers having a functional group. Body (b) is mentioned. The copolymerizable compound (C
) in the copolymer is 0 to 90% by weight from the viewpoint of processability, mechanical strength, etc.

Examples of the vinyl cyanide compound (a) include acrylonitrile, methacrylaterile, α-chloroacrylonitrile, and the like, and among these, acrylonitrile is particularly preferred.

The content of vinyl cyanide compound (a) in the copolymer is preferably 10 to 55% by weight, more preferably 20 to 4% by weight.
It is 5% by weight. If this amount is less than 10% by weight, the heat aging resistance and mechanical strength of the resulting copolymer may decrease, and if it exceeds 55% by weight, the rubbery properties may be poor and processability may be poor. .

The above α,β unsaturated carboxylic acid ester Φ) has the general formula (I
II) (In the formula, R7 is hydrogen or a methyl group, and R8 has 1 to 1 carbon atoms.
12 alkyl group), and specific examples include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, n-hexyl acrylate, and n-hexyl acrylate. -n-octyl, 2-ethyl-hexyl acrylate, dodecyl acrylate, 2-methoxyethyl acrylate, methyl methacrylate, n-butyl methacrylate, n-octyl methacrylate, 2-ethyl methacrylate -hexyl, n-dodecyl methacrylate, and the like. Among these, methyl acrylate, ethyl acrylate, acrylic acid-n-
Butyl, n-ethyl-hexyl acrylate, ethyl methacrylate, n-butyl methacrylate and 2-ethyl-hexyl methacrylate are preferred;
Particularly preferred are n-butyl and ethyl acrylate.

The content of the α,β unsaturated carboxylic acid ester (b) in the copolymer is preferably 10 to 70% by weight.

If it exceeds 70% by weight, processability may be poor.

Examples of the crosslinkable monomer (C) include aromatic compounds such as divinylbenzene and 1.3.5-)divinylbenzene; ester compounds such as diallyl phthalate and diallyl fumarate; trimethylolpropane trimethacrylate and ethylene glycol. Acrylic acid esters such as dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate can be mentioned.

The content of the crosslinkable monomer (C) in the copolymer is preferably 0 to 10% by weight, more preferably 0 to 5% by weight.

A copolymer imparted with a gel by this crosslinkable monomer has excellent surface texture and dimensional stability when molded into a product, but if this amount exceeds 10% by weight, the copolymer becomes brittle and mechanically The strength of the target may be poor.

Examples of the monomer (a) containing the above-mentioned functional group include monomers having a carboxyl group, such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, or acid anhydrides thereof;
Tertiary amino group-containing monomers such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and dibutylaminoethyl (meth)acrylate; 1-hydroxypropyl (meth)acrylate, 2-
Examples include monomers having a hydroxyl group such as hydroxypropyl (meth)acrylate and hydroxyethyl (meth)acrylate; monomers having an epoxy group such as glycidyl (meth)acrylate, allyl glycidyl ether, and vinyl glycidyl ether. These functional group-containing monomers can be used alone or in combination of two or more.

The content of the functional group-containing monomer (d) in the copolymer is preferably 0 to 20% by weight, more preferably 0.1 to 1% by weight.
It is 0% by weight. If it is 20% by weight or more, the glass transition temperature of the copolymer rubber may become high, resulting in poor cold resistance.

The polymerization method for the above copolymer is not particularly limited, and can be produced, for example, by conventional emulsion polymerization, suspension polymerization, bulk polymerization, or solution polymerization in the presence of a radical polymerization initiator. The polymerization method can be either continuous or batchwise.

Examples of emulsifiers used in the production by emulsion polymerization include alkyl sulfates and alkylaryl sulfonates.

Examples of radical initiators for initiating polymerization include organic peroxides such as benzoyl peroxide, cumene hydroperoxide, and paramenthane hydroperoxide, azo compounds represented by azobisisobutyronitrile, and potassium persulfate. , inorganic persulfates such as ammonium persulfate, and redox catalysts typified by a combination of organic peroxide and iron sulfate. These radical initiators are usually used in an amount of 0.01 to
2% by weight is used.

A molecular weight regulator may be used as necessary, and specific examples thereof include t-dodecylmercaptan, dimethylxanthogen disulfide, and the like.

The copolymerization reaction is carried out at a temperature of -100 to 200°C, preferably 0°C.
It can be carried out under conditions of ~60°C.

After reaching a predetermined polymerization conversion rate, a reaction terminator such as N,N-diethylhydroxylamine is added to stop the polymerization reaction, and unreacted monomers in the resulting latex are removed by steam distillation. A copolymer can be obtained by removing the latex, adding anti-aging agents such as phenols and amines, and further mixing with an aqueous solution of metal salts such as an aqueous solution of aluminum sulfate and an aqueous solution of calcium chloride to coagulate the latex and drying it. .

When producing by suspension radical polymerization, add saponified polyvinyl alcohol as a dispersant, perform polymerization using an oil-soluble radical initiator such as azobisisobutyronitrile, benzoyl peroxide, etc. , a copolymer can be obtained by removing water.

Also when producing by solution radical polymerization, general known methods can be employed.

The molecular weight of the copolymer can be adjusted by changing reaction conditions such as the type and amount of the molecular weight regulator, the type and amount of the radical initiator, the polymerization temperature, the type and amount of the solvent, and the monomer concentration. Mooney viscosity MLl+4 (100℃) is 1
0 to 150, preferably 20 to 120. If the Mooney viscosity of the copolymer is less than 10, the mechanical strength of the copolymer will be poor, and if it exceeds 150, the processability of the copolymer will be reduced.

In copolymers obtained using polyfunctional monomers,
Preferably, the gel content is 20% by weight or more. When the copolymer is mixed with another polymer, especially a thermoplastic resin or a thermosetting resin, good dispersibility is obtained when the gel content is 20% by weight or more.

Moreover, the compound (A) of the present invention can be blended with a rubbery polymer (polymer having rubber elasticity) and used as a rubber composition.

In addition to the copolymer of the present invention, examples of the rubbery polymer include natural rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, polyisoprene rubber, butyl rubber,
Examples include acrylonitrile-butadiene copolymer rubber, chloroprene rubber, ethylene-propylene-(diene) copolymer rubber, acrylic rubber, epichlorohydrin rubber, fluororubber, chlorinated polyethylene rubber, and urethane rubber. Among these, particularly preferred are the copolymer of the present invention and the acrylonitrile-butadiene copolymer rubber.

The compounding amount of compound (A) is 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the rubbery polymer.
Parts by weight. If this amount is less than 0.1 parts by weight, the effect of improving the weather resistance of the resulting rubber composition will not be sufficient, and if it exceeds 10 parts by weight, the mechanical strength will deteriorate.

The copolymer and rubber composition of the present invention described above can be made into a crosslinked product using a crosslinking agent.

In the case of diene copolymers such as acrylonitrile-butadiene copolymer, natural rubber, polyisoprene, polybutadiene, and styrene-butadiene copolymer, the crosslinking agent is mainly sulfur, organic sulfur-containing compounds, and organic peroxide. In the case of chloroprene rubber and chlorosulfonated polyethylene, metal oxides are used, and in the case of butyl rubber, sulfur, quinone dioxime, modified alkylphenol resin, etc. are used, and ethylene-propylene- In the case of (diene) copolymer rubber, sulfur, organic peroxide, etc. are used, and in the case of urethane rubber, polyisocyanate, polyamine,
Organic peroxides and the like are used.

As the sulfur, powdered sulfur, precipitated sulfur, colloidal sulfur, insoluble sulfur, highly dispersed sulfur, etc. are used.

The organic sulfur-containing compound is a compound that releases active sulfur by thermal dissociation, and includes, for example, tetramethylthiuram disulfide and 4,49-dithiomorpholine, which are thiuram promoters.

Examples of organic peroxides include 2,5-dimethyl-2゜5-di(t-butylperoxy)hexane, 2゜5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,
3-bis(t-butylperoxy)-isopropylbenzene, dicumyl peroxide, dibutyl peroxide, 1.1-di-t-butylperoxy-3,3,5-
Trimethylcyclohexane, t-butylcumyl peroxide, t-butylperoxy-isopropyl carbonate, etc. are used.

Examples of metal oxides include zinc oxide, magnesium oxide, and lead oxide.

Examples of the quinone dioxime include p-quinone dioxime and P,P''-dibenzoylquinone oxime.

Examples of modified alkylphenol resins include alkylphenol formaldehyde resins and brominated alkylphenol formaldehyde resins.

The copolymer and rubber composition of the present invention described above can also be mixed with a thermoplastic resin and used as a thermoplastic elastomer.

The thermoplastic resin is not particularly limited, and for example, polypropylene, vinyl chloride resin, polyester resin, polyamide resin, styrene resin, polycarbonate resin, etc. can be used. Among these, vinyl chloride resin is particularly preferred.

The amount of thermoplastic resin blended is not particularly limited, but is 10 to 1000 parts by weight per 100 parts by weight of the copolymer or rubber composition.
Parts by weight are preferred. If the amount of thermoplastic resin is less than 10 parts by weight, mechanical strength will be poor, and if it exceeds 1000 parts by weight, the composition may lose its rubber-like elasticity and have poor processability.

There is no particular restriction on the method of mixing with the thermoplastic resin, and known methods such as an open type mixing roll, a non-release type Banbury mixer 1 extruder, and a kneader 1 continuous mixer can be used.

The rubber-like elastomer composition in which a crosslinking agent or a thermoplastic resin is blended with the copolymer or rubber composition of the present invention may include, for example, carbon black, calcium carbonate, Calcium silicate, clay, kaolin, talc, silica, diatomaceous earth, mica powder,
Fillers such as asbestos, alumina, barium sulfate, aluminum sulfate, calcium sulfate, basic magnesium carbonate, molybdenum disulfide, graphite, carbon fiber, glass fiber; for example, ultramarine, titanium oxide, zinc white, red iron, navy blue, azo pigments, Coloring agents such as nitroso pigments, lake pigments, and phthalocyanine pigments can be blended.

Also, mineral oil-based rubber softeners called process oils or extender oils, dioctyl phthalate, dibutyl phthalate, diethyl phthalate, dimethyl phthalate, tricresyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, trimellitic acid. Plasticizers such as esters, dioctyl adipate, dioctyl azelaate, dioctyl sebacate, epoxy fatty acid esters, liquid rubbers such as liquid NBR1 liquid acrylic rubber, liquid polybutadiene rubber, benzenesulfonate butylamide, product name manufactured by Yoshitomi Pharmaceutical Co., Ltd. POBO 1 A plasticizer for nylon such as Sunsocizer N400 (trade name, manufactured by Shin Nippon Rika Co., Ltd.) may be blended within a range that does not impair mechanical strength to improve fluidity.

Furthermore, during mixing, phenylenediamine-based antioxidants (product names manufactured by Iriuchi Shinko Kagaku Kogyo Co., Ltd., such as Tsukuraq CD1, Tsukurac TD, Tsukurac G1, Tsukurac WHITE, etc.), imidazole-based antioxidants (product names made by Iriuchi Shinko Kagaku Kogyo Co., Ltd., Tsukurak MB, etc.), Tsukrac MMB, etc.), hindered phenolic antioxidants (product name: BHT, manufactured by Sumima Kagaku Co., Ltd.),
It is possible to add products such as TSKURANK 300 manufactured by Iriuchi Shinko Kagaku Kogyo Co., Ltd.).

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.

Analysis and measurement of physical properties were carried out by the following methods.

<Infrared analysis> Measurement was carried out by the KBr tablet method using an A-11I type device manufactured by JASCO Corporation.

<Measurement of physical properties> The composition was press-molded, and the physical properties of the obtained sheet were determined according to JIS
Measured according to K6301.

<Weather Resistance Test> Physical properties were evaluated after exposure to a black panel temperature of 63° C. or 83° C. for a predetermined time using a sunshine weather meter.

(Presence or absence of migration of anti-aging agent to the surface of the sample) In the weather resistance test, after exposure for a predetermined time, the presence or absence of migration of the anti-aging agent to the surface of the sample was visually examined.

<Measurement of gel content> Accurately weigh 1 g of copolymer, and add 100 mj of methyl ethyl ketone.
! After leaving it for 24 hours at room temperature, it was filtered through a 200-mesh wire mesh, the insoluble matter was dried under reduced pressure, and its weight was accurately weighed.
The ratio of the amount of insoluble matter to the amount charged was determined.

Example 1 0.5 mole diallylamine and 2.0 wt% NaOH
0.55 mol of carbon disulfide was added dropwise to a solution of 1.022 g (0.5 mol) of an aqueous solution at 30°C to react, and then a solution of 0.25 mol of nickel sulfate dissolved in 400 ml of water was added to this solution. was added dropwise at 30°C to complete the reaction. The formed crystals were collected by filtration and dried under reduced pressure at 50°C for 48 hours to obtain bis(
Diallyldithiocarbamic acid) nickel was obtained. The yield was 71%.

This nickel bis(diallyldithiocarbamate) was a yellow-green powder, with a melting point of 116.5-119.0°C and a decomposition temperature of 302°C. Also, the amount of Ni contained is 15.0
1% (theoretical amount 14.56%).

FIG. 1 is an infrared absorption spectrum diagram of the obtained product. This figure shows 2850am-', 2930cta-'
, absorption due to C-H stretching vibration at 2960 cm-',
C=C stretching vibration in 1640C11-', 1510el
-'C-N stretching vibration and 1470cm-'10-
3 absorption peaks attributed to stretching vibrations were observed.

Example 2 The following polymerization compound was placed in an autoclave having an internal volume of 202 cm, and emulsion polymerization was carried out at a polymerization temperature of 20°C. Note that nickel bis(diallyldithiocarbamate) was dissolved in acrylonitrile and charged.

Butadiene 58 parts by weight Acrylonitrile 40 Water 00 Tertiary dodecyl mercaptan 0. O25 Potassium phosphate 0.3 Ferrous sulfate
0. OO5 After the polymerization conversion rate reached 90%, 0.2 parts by weight of hydroxylamine sulfate per 100 parts by weight of monomer was added to stop the polymerization. The obtained polymerization product was heated and steam distilled under reduced pressure at about 70°C to recover residual monomers, and then 1 part by weight of alkylated phenol was added as an antiaging agent and unreacted monomers were removed by steam distillation. The polymer was removed and calcium chloride was added to coagulate the polymer. Next, this polymer was washed with water and dried using a vacuum dryer to obtain copolymer (1). Table 1 shows the composition and measurement results of physical properties (Mooney viscosity and gel content) of this copolymer (1).

Furthermore, after removing unreacted substances from the copolymer (1) by alcohol extraction, an infrared absorption spectrum was measured to confirm the structure. The infrared absorption spectrum is shown in Figure 2, and the stretching vibration of the nitrile group is at 2250 cm-', and the stretching vibration is at 920 cm-'.
bending vibration of the carbon-carbon double bond at cm-' and 970 cm-' and > of thiocarbamic acid at 1640CIl-'
C=S stretching vibration was observed.

Below are blank spaces Examples 3 to 5 Copolymerization was carried out in the same manner as in Example 2 except that nickel bis(diallyldithiocarbamate) obtained in Example 1 was used and the composition of the copolymer (U) shown in Table 1 was used. Synthesize the union,
Its physical properties were measured and the results are shown in Table 1.

Next, using the copolymer (I) obtained in Example 2 and the copolymer (n) obtained above, the respective formulations shown in Table 2 were kneaded with a roll to form a new copolymer. A composition was obtained. These compositions were press-cured at 160°C for 20 minutes to obtain a crosslinked product, and the physical properties and weather resistance of this crosslinked product (black panel temperature 63°C, 1120 hours and 360 hours exposure)
The migration of the anti-aging agent to the surface was investigated and the results are shown in Table 2.

Comparative Example 1.2 Using the same reaction method as in Example 2, the copolymers shown in Table 1 (
A copolymer was synthesized in the same manner as in Example 2 except that the compositions i) and (ii) were used, and its physical properties were measured. The results are shown in Table 1.

Next, using the obtained copolymers (i) and (ii),
A copolymer composition was prepared in the same manner as in Example 3 using each of the formulations shown in Table 2, and the physical properties, weather resistance, and migration of the anti-aging agent to the surface of the crosslinked product were examined, and the results are shown in Table 2. It was shown to.

Comparative Example 3 Comparative Example 2 with the anti-aging agent NOCRACNBC (trade name, manufactured by Ohmukai Shinko Kagaku Co., Ltd.) was evaluated in the same manner as Comparative Example 2, and the results are shown in Table 2.

From the results in Table 2 in the margin below, it can be seen that compositions containing a copolymer using the compound (A) of the present invention and the compound (^) (Examples 3 to 3)
It can be seen that sample 5) has excellent weather resistance compared to the conventional composition (Comparative Example 1.2), has less migration of the anti-aging agent to the surface, and is an excellent composition without staining. In addition, in the case of adding the conventional carbamate-based anti-aging agent NBC (Comparative Example 3)
) does not improve surface migration.

Examples 6 to 12 Copolymers were synthesized in the same manner as in Example 2 except that the compositions of copolymers (II[), (IV), (V) and (Vl) shown in Table 1 were used. The physical properties were measured and the results are shown in Table 1.

Next, using the obtained copolymers (I[I), (IV), (V) and (VI), thermoplastic resin compositions were prepared according to the formulations shown in Table 3, respectively. This composition is made by adding vinyl chloride resin, tribasic lead sulfate, and a plasticizer (dioctyl phthalate (DOP)) and stirring at high speed in a Henschel mixer until the contents are homogeneous, then adding other ingredients. The product was further stirred.

The obtained vinyl chloride resin composition was kneaded for 10 minutes at 180°C using two 6-inch rolls, and then press-molded to improve the physical properties and weather resistance of the molded product (black panel temperature 8
(300 hours exposure at 3° C.), the migration of anti-aging agent to the surface was investigated and the results are shown in Table 3.

Comparative Examples 4-8 Copolymers (in), (iv) and (V) shown in Table 1
A copolymer was synthesized in the same manner as in Example 2 except that the composition was as follows. The physical properties were measured and the results are shown in Table 1.

Next obtained copolymers (ii), (iv) and (V)
A vinyl chloride resin composition was prepared in the same manner as in Example 6 using the formulations shown in Table 3, which were press-molded, and the properties of the molded products were examined in the same manner. The results are shown in Table 3. Indicated.

From the results in Table 3 below, it can be seen that the composition (Example 6 .8.10.1
A composition (Example 7.9.12) in which the compound (A) of the present invention and a thermoplastic resin are blended with 1) and copolymer (iii) or (iv) is different from conventional compositions (Comparative Examples 4 to 4). It can be seen that this composition has excellent weather resistance compared to 8), has less migration of the anti-aging agent to the surface, and is free from staining.

Comparative Example 9 In Example 1, by using copper sulfate instead of nickel sulfate, bis(diallyldithiocarbamic acid)
Obtained copper. Yield is 64%, melting point is 95.5-97
．． The temperature was 5°C. The same evaluation as in Example 9 was performed using this compound in place of nickel bis(diallyldithiocarbamate). The results are shown in Table 4.

Comparative Example 10 In Example 1, zinc sulfate was used instead of nickel sulfate to obtain zinc bis(diallyldithiocarbamate). The yield was 55%. The same evaluation as in Example 9 was performed using this compound in place of nickel bis(diallyldithiocarbamate). The results are shown in Table 4.

Comparative Example 11 In Example 1, nickel bis(monoallyldithiocarbamate) was obtained by using monoallylamine instead of diallylamine.

The yield was 72%, and the melting point was 139.5-141.0°C. The same evaluation as in Example 9 was performed using this compound in place of nickel bis(diallyldithiocarbamate). The results are shown in Table 4.

Table 4 [Effects of the Invention] According to the copolymer or rubber composition using the dithiocarbamate compound of the present invention, excellent weather resistance can be imparted to a rubber-like elastic body even at high temperatures. Further, even when the compound of the present invention is contained in a rubber elastic body, the compound does not migrate to the surface of the elastic body.

Therefore, the dithiocarbamate compound of the present invention can be used in automobile parts such as body panels, bumper parts, molesite shields, glass launch channels, weather strips, side moldings, steering wheels, jib-int boots, strut suspension boot handles, and shoes. Soles, footwear such as sandals, electric wire coverings, connectors, cap plugs, electrical parts such as gears, golf club grips, baseball bat grips, car and motorcycle grips, swimming fins, swimming goggles and other leisure goods, galkerato, waterproofing It is particularly useful as an anti-aging agent for cloth, thick hoses, fuel hoses, freon hoses, power steering hoses, coil guppies, backings, sealants, rolls, garden hoses, belts, vibration damping materials for damping steel plates, various cushioning agents, etc.

[Brief explanation of drawings]

FIG. 1 is an infrared absorption spectrum diagram of the compound of the present invention [nickel bis(diallyldithiocarbamate)], and FIG. 2 is an infrared absorption spectrum diagram of the copolymer of the present invention.

Claims (3)

[Claims] (1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are the same or different hydrogen atoms or alkyl groups having 1 to 4 carbon atoms, R A dithiocarbamate compound represented by ^3 means an alkylene group having 1 to 3 carbon atoms. (2) A dithiocarbamate compound (A) represented by the general formula (I) according to claim (1), a conjugated diene compound (
B) and other compounds copolymerizable with these (C),
0 each for the total amount of (A), (B) and (C)
．． 1-5% by weight, 5-80% by weight and 0-90% by weight
A copolymer obtained by polymerizing at a ratio of
A copolymer having a molecular weight of 0 to 150. (3) A rubber composition comprising 100 parts by weight of a rubbery polymer and 0.1 to 10 parts by weight of the dithiocarbamate compound (A) according to claim (1).