JP2003138077A - Rubber composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel vulcanization accelerator which can take the place of general-purpose vulcanization accelerators which have been heretofore used for a halogen-containing saturated rubber. SOLUTION: The vulcanization accelerator for a halogen-containing saturated rubber comprises a carboxylic acid amine salt which has not been heretofore used as a vulcanization accelerator for a halogen-containing saturated rubber. Use of the vulcanization accelerator permits efficient and effective crosslinking of the rubber. The vulcanizable halogen-containing saturated rubber composition has the vulcanization accelerator incorporated thereinto. A vulcanizate thereof is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to sulfur and tetramethylene thiuram disulfide, N, N′-cyclohexyl-2-benzothiazolyl sulfenamide, zinc dimethyldithiocarbamate, etc., which have been conventionally used for halogenated saturated rubber. The present invention relates to a novel vulcanization accelerator which replaces a combined vulcanization system. More specifically, the present invention relates to a vulcanization accelerator containing an amine salt of a carboxylic acid and a rubber composition containing the vulcanization accelerator. More specifically, by vulcanizing the vulcanization accelerator, physical properties such as tensile strength and elongation are improved. The present invention relates to an excellent rubber composition.

[0002]

2. Description of the Related Art As a vulcanizing agent for halogen-based saturated rubber,
Chlorosulfonated polyethylene (hereinafter referred to as CSM)
Include dipentamethylene thiuram tetrasulfide,
Epichloridohydrin rubber (hereinafter referred to as CHR) contains ethylene thiourea and sulfur-dicatecholborate di-
o-Triguanidine salt and dibenzothiazyl disulfide are used for chlorinated polyethylene (hereinafter referred to as CPE) such as ethylenethiourea, hexamethylenediaminecarbamate, ethylenediaminecarbamate, N, N'-dicinnamylidene-1,6-hexamethylenediamine, etc. However, for chlorinated butyl rubber (hereinafter referred to as CIIR), tetramethylthiuram disulfide and dibenzothiazyl disulfide, etc., and for fluororubber (hereinafter referred to as FKM), N, N '
-Dicinnamylidene-1,6-hexamethylenediamine and the like are used alone or in combination with a metal compound. However, there have been no examples of using the amine salt of carboxylic acid of the present application as a vulcanization accelerator.

[0003]

SUMMARY OF THE INVENTION The object of the present invention is to provide tetramethylene thiuram disulfide and N, N'-cyclohexyl-2-, which have been conventionally used for halogenated saturated rubber.
It is intended to provide a novel vulcanization accelerator which replaces a general-purpose vulcanization accelerator in which benzothiazolylsulfenamide, zinc dimethyldithiocarbamate and the like are combined with sulfur.

[0004]

[Means for Solving the Problems] The inventors of the present invention have made extensive studies to solve the above problems, and as a result, amine salts of carboxylic acids that have not been used as vulcanization accelerators for halogenated saturated rubbers. It was found that the rubber can be crosslinked efficiently and effectively by using a vulcanization accelerator containing the present invention, and the present invention has been completed. That is, the present invention is
It is a vulcanization accelerator for rubber containing an amine salt of a carboxylic acid.

The present invention is also a vulcanizable halogen-based saturated rubber composition containing the above-mentioned vulcanization accelerator.

The halogen-based saturated rubber of the present invention is a rubber having a halogen group in the side chain and a small number of unsaturated bonds in the main chain. Specifically, it is chlorosulfonated polyethylene, epichloridhydrin rubber, chlorine. It is one or more selected from chlorinated polyethylene, chlorinated butyl rubber, and fluororubber. Further, the present invention is a vulcanized product obtained by vulcanizing the above rubber composition.

The present invention will be described in more detail below. The compound used in the present invention can be obtained as an amine salt compound of a carboxylic acid composed of an aliphatic amine or an aromatic amine and an aromatic carboxylic acid or an aliphatic carboxylic acid.

Aromatic carboxylic acid compounds and aliphatic carboxylic acid compounds constituting the amine salt of carboxylic acid used in the present invention include benzoic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, Azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, 1,11-undecanedicarboxylic acid, tetradodecanedioic acid, pentadodecanedioic acid, hexadodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2- Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic acid, cyclooctane-1,2-dicarboxylic acid, cyclooctane-1,3-dicarboxylic acid, cyclooctane-1, 4-dicarboxylic acid, cyclooctane-1,
5-dicarboxylic acid, ethylene-diamine-tetraacetic acid, hydroxyethyl-ethylene-diamine-tetraacetic acid, nitrilo-triacetoacetic acid, diethylene-triamine-pentaacetic acid, triethylene-tetramine-hexaacetic acid, dicarboxymethyl-glutamic acid, hydroxyl- Iminodiacetic acid, iminodiacetic acid, dihydroxyethyl-glycine,
Examples include 1,3-propanediamine-tetraacetic acid and 1,3-diamino-2-hydroxypropane-tetraacetic acid.

The aliphatic amine and aromatic amine compounds constituting the amine salt of carboxylic acid used in the present invention include methylamine, ethylamine, propylamine, isopropylamine, butylamine, t-butylamine,
Pentylamine, hexylamine, 2-ethylhexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine, hexadecylamine, 1-aminooctadecane, aniline, benzylamine, diphenylamine, cyclopropyl Amine, dicyclopropylamine, cyclobutylamine, dicyclobutylamine,
Cyclopentylamine, dicyclopentylamine, cyclohexylamine, dicyclohexylamine, cycloheptylamine, dicycloheptylamine, cyclooctylamine, dicyclooctylamine, 2-aminotoluene, 3-aminotoluene, 4-aminotoluene, 2,4
-Dimethylaniline, 2,3-dimethylaniline, 2,
5-dimethylaniline, 2,6-dimethylaniline,
3,4-dimethylaniline, 3,5-dimethylaniline, 2,4,5-trimethylaniline, 2,4,6-trimethylaniline, 2,3,4,5-tetramethylaniline, 2,3,5 6-tetramethylaniline, 2,
3,4,6-tetramethylaniline, 2-ethyl-3-
Hexylaniline, 2-ethyl-4-hexylaniline, 2-ethyl-5-hexylaniline, 2-ethyl-
6-hexylaniline, 3-ethyl-4-hexylaniline, 3-ethyl-5-hexylaniline, 3-ethyl-2-hexylaniline, 4-ethyl-2-hexylaniline, 5-ethyl-2-hexylaniline, 6-ethyl-2-hexylaniline, 4-ethyl-3-hexylaniline, 5-ethyl-3-hexylaniline, 1,2
-Phenylenediamine, 1,3-phenylenediamine,
1,4-phenylenediamine, 2-aminobenzylamine, 3-aminobenzylamine, 4-aminobenzylamine, 2- (4-aminophenyl) ethylamine, 2-
(3-Aminophenyl) ethylamine, 2- (2-aminophenyl) ethylamine, 2,3-diaminotoluene, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 3,4- Diaminotoluene, 2,3-dimethyl-p-phenylenediamine,
2,5-dimethyl-p-phenylenediamine, 2,6-
Dimethyl-p-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,5-dimethyl-m-phenylenediamine, 2,6-dimethyl-m-phenylenediamine, 4,5-dimethyl-m-phenylenediamine , 3,4-dimethyl-o-phenylenediamine, 3,
5-dimethyl-o-phenylenediamine, 3,6-dimethyl-o-phenylenediamine, 1,3-diamino-
2,4,6-trimethylbenzene, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,4
5,6-tetramethyl-1,3-phenylenediamine,
3,4,5,6-tetramethyl-1,2-phenylenediamine, 2,4-diamino-3,5-diethyltoluene, 2,3-diamino-4,5-diethyltoluene,
2,4-diamino-4,6-diethyltoluene, 2,3
-Diamino-5,6-diethyltoluene, 2,4-diamino-3,6-diethyltoluene, 2,5-diamino-
3,4-diethyltoluene, 2,5-diamino-3,6
-Diethyltoluene, 2,5-diamino-4,6-diethyltoluene, 2,3-diamino-4,5-diethyltoluene, 2,3-diamino-4,6-diethyltoluene, 2,3-diamino-4 , 5,6-Triethyltoluene, 2,4-diamino-3,5,6-triethyltoluene, 2,5-diamino-3,4,6-triethyltoluene, 2-methoxyaniline, 3-methoxyaniline, 4
-Methoxyaniline, 2-methoxy-3-methylaniline, 2-methoxy-4-methylaniline, 2-methoxy-5-methylaniline, 2-methoxy-6-methylaniline, 3-methoxy-2-methylaniline, 3 -Methoxy-4-methylaniline, 3-methoxy-5-methylaniline, 3-methoxy-6-methylaniline, 4-methoxy-2-methylaniline, 4-methoxy-3-methylaniline, 2-ethoxyaniline, 3 -Ethoxyaniline, 4-ethoxyaniline, 4-methoxy-5-methylaniline, 4-methoxy-6-methylaniline, 2-methoxy-3-ethylaniline, 2-methoxy-4-ethylaniline, 2-methoxy-5. -Ethylaniline, 2-
Methoxy-6-ethylaniline, 3-methoxy-2-ethylaniline, 3-methoxy-4-ethylaniline, 3
-Methoxy-5-ethylaniline, 3-methoxy-6-
Ethylaniline, 4-methoxy-2-ethylaniline,
4-methoxy-3-ethylaniline, 2-methoxy-
3,4,5-trimethylaniline, 3-methoxy-2,
4,5-trimethylaniline, 4-methoxy-2,3
Examples include 5-trimethylaniline.

The carboxylic acid amine compound used in the present invention includes isophthalic acid disubstituted propylamine salt, isophthalic acid monosubstituted propylamine salt, isophthalic acid disubstituted ethylamine salt, isophthalic acid monosubstituted ethylamine salt, and isophthalic acid. 2-substituted methylamine salt of acid, 1-substituted methylamine salt of isophthalic acid, 2-substituted propylamine salt of adipic acid, 2-substituted ethylamine salt of adipic acid,
2-substituted methylamine salt of adipic acid, 1-substituted propylamine salt of adipic acid, 1-substituted ethylamine salt of adipic acid, 1-substituted methylamine salt of adipic acid, 4-substituted propylamine salt of ethylenediaminetetraacetic acid, 3 of ethylenediaminetetraacetic acid Substituted propylamine salt, 2-substituted propylamine salt of ethylenediaminetetraacetic acid, 1-substituted propylamine salt of ethylenediaminetetraacetic acid, 4-substituted ethylamine salt of ethylenediaminetetraacetic acid, 3-substituted ethylamine salt of ethylenediaminetetraacetic acid, 2-substituted ethylamine of ethylenediaminetetraacetic acid Salt, monosubstituted ethylamine salt of ethylenediaminetetraacetic acid, tetrasubstituted methylamine salt of ethylenediaminetetraacetic acid, trisubstituted methylamine salt of ethylenediaminetetraacetic acid, ethylenediamineteto 2-substituted methylamine salt of acetic acid, 1-substituted methylamine salt of ethylenediaminetetraacetic acid, 5-substituted methylamine salt of diethylenetriaminepentaacetic acid,
4-substituted methylamine salt of diethylenetriaminepentaacetic acid, 3-substituted methylamine salt of diethylenetriaminepentaacetic acid, 2-substituted methylamine salt of diethylenetriaminepentaacetic acid, 1-substituted methylamine salt of diethylenetriaminepentaacetic acid, 5 of diethylenetriaminepentaacetic acid
Substituted ethylamine salt, 4-substituted ethylamine salt of diethylenetriaminepentaacetic acid, 3-substituted ethylamine salt of diethylenetriaminepentaacetic acid, 2-substituted ethylamine salt of diethylenetriaminepentaacetic acid, 1-substituted ethylamine salt of diethylenetriaminepentaacetic acid, 5-substituted propylamine salt of diethylenetriaminepentaacetic acid, 4-substituted propylamine salt of diethylenetriaminepentaacetic acid, 3-substituted propylamine salt of diethylenetriaminepentaacetic acid, 2-substituted propylamine salt of diethylenetriaminepentaacetic acid, 1-substituted propylamine salt of diethylenetriaminepentaacetic acid, 2-substituted propylamine salt of nitriloacetic acid, nitrilo Acetic acid monosubstituted propylamine salt, nitriloacetic acid disubstituted ethylamine salt, nitriloacetic acid monosubstituted ethylamine salt, 2-substituted methylamine salt of Lilo acetate,
Nitriloacetic acid monosubstituted methylamine salt, iminodiacetic acid disubstituted propylamine salt, iminodiacetic acid monosubstituted propylamine salt, iminodiacetic acid disubstituted ethylamine salt, iminodiacetic acid monosubstituted ethylamine salt, iminodiacetic acid Of 2
Examples thereof include a substituted methylamine salt and a monosubstituted methylamine salt of iminodiacetic acid.

The carboxylic acid amine salt compound used in the present invention has at least one amine salt, may be two or more amine salts, and may have a carboxyl group remaining.

The amount of amine salt compound of carboxylic acid added to the rubber composition of the present invention is 0.01 to 20 parts by mass, preferably 0.1 to 10 parts by mass per 100 parts by mass of rubber.
It is preferably within the range of parts by mass. In addition, all parts are made of rubber 10 except as otherwise noted in this specification.
Parts per 0 parts by weight (parts by weight), and percentages are by weight of the total composition.

The rubber composition of the present invention includes beryllium, magnesium, zinc, calcium, cadmium, strontium, barium, germanium, titanium, tin, zirconium, lead, antimony, vanadium, arsenic, bismuth, chromium, molybdenum, tungsten, Elemental elements such as tellurium, selenium, iron, nickel, cobalt, and osmium, and metal compounds such as oxides and hydroxides of the above elements are used as necessary.

In the rubber composition of the present invention, various additives conventionally used in rubbers and plastics can be compounded so as to reach the respective target physical properties depending on the application. Examples of these additives include a reinforcing agent, a softening agent, a processing aid, and an antiaging agent.

Examples of the reinforcing agent include carbon black and silica, which are used to increase the mechanical strength of rubber. The addition amount of the reinforcing agent is generally about 20 to 80 parts by mass with respect to 100 parts by mass of rubber. Further, fillers such as calcium carbonate, clay and talc can be added if necessary.

Examples of the softening agent include petroleum-based softening agents such as lubricating oil, process oil, paraffin, liquid paraffin, petrolatum and petroleum asphalt, and fatty oil-based softening agents such as rapeseed oil, linseed oil, castor oil and coconut oil. Rubber 10
Up to about 40 parts by weight can be added to 0 parts by weight.

Examples of the processing aid include fatty acids such as stearic acid, which can be added up to about 0.5 to 5 parts by mass with respect to 100 parts by mass of rubber.

Examples of the antioxidant include amine-based, imidazole-based, metal carbamate, phenol-based, and wax-based antioxidants, which are added in an amount of about 0.5 to 10 parts by mass per 100 parts by mass of rubber. be able to.

Since the rubber composition of the present invention has good processability, the rubber composition is mixed by a kneader such as a kneader, Banbury or roll in the same manner as ordinary rubber, and molded into a shape according to the purpose. A vulcanized product can be obtained.
Specifically, each component is kneaded at a temperature not higher than the vulcanization temperature, and then the mixture is molded into various shapes and vulcanized to obtain a vulcanized product. The temperature during vulcanization and the vulcanization time can be appropriately set. The vulcanization temperature is preferably 130 to 200 ° C, and 140 to
190 ° C. is particularly preferred.

[0020]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples. Examples and Comparative Examples Vulcanized products of rubber compositions obtained by adding the vulcanization accelerators described in Table 2 in the amounts shown in Table 2 according to the compounding recipe shown in Table 1 and compounding using an 8-inch roll. Conduct physical property tests,
The results are shown in Table 1. Mechanical properties such as tensile strength and elongation were measured according to JIS K6251 using a test piece vulcanized by a hydraulic press at 160 ° C. for 30 minutes. The hardness was measured according to JIS K6253 using a durometer hardness meter. Further, a vulcanization system conventionally used as a vulcanization accelerator was used for the same test, and the results are shown in Table 1 as a comparative example.

The Mooney Scorch test is JIS K63
Test temperature 1 using L-type rotor according to 00
The minimum value (Vm) of Mooney viscosity and scorch time (MLt5) at 25 ° C. were measured.

The vulcanization test by the vibration type vulcanization tester is conducted by TOYO SEIKI AUTOMATIC ROTORLESS RH.
Measurement was performed at 160 ° C. using EOMETER ALR-2, and the minimum torque (M
L) and maximum torque (MH) were determined.

[0023]

[Table 1]

[0024]

[Table 2]

The CSM (320) used in Table 1 is chlorosulfonated polyethylene rubber (CSM) manufactured by Denki Kagaku Kogyo Co., Ltd. The epichromer CG used in Table 1 is
It is an epiclide hydrin rubber manufactured by Daiso Corporation. The MgO used in Table 1 is manufactured by Kyowa Chemical Industry Co., Ltd., and Kyowamag 150. The ZnO used in Table 1 is manufactured by Sakai Chemical Industry Co., Ltd. and the two kinds of zinc white are SRF used in Table 1. 50 FEF used in Table 1 is Asahi Carbon Co., Ltd., # 60 TT used in Table 2 is Ouchi Shinko Kagaku Kogyo Co., Ltd., PZ used in Table 2 is Ouchi Shinko Chemical Co., Ltd. Manufactured by Ouchi Shinko Chemical Industry Co., Ltd., the amine salt used in Table 2 is a disubstituted propylamine salt of isophthalic acid.

[0026]

As shown in the examples, the novel vulcanization accelerator comprising the amine salt compound of carboxylic acid of the present invention is added to CSM.
As a result of applying it to CHR and CHR, it was confirmed to have vulcanizability.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) // B29K 19:00 B29K 19:00 105: 24 105: 24 F term (reference) 4F203 AA45A AB03 DA11 DC01 4J002 BB241 BB271 BD121 CH041 DE077 DE107 EF006 EN006 EN026 EN066 FD010 FD020 FD030 FD156 GT00

Claims (5)

[Claims] 1. A vulcanization accelerator for a halogen-based saturated rubber, which comprises a compound consisting of a salt of a carboxylic acid and an amine. 2. The vulcanization accelerator for rubber according to claim 1, wherein the amine is at least one selected from aliphatic amines and aromatic amines. 3. The vulcanization accelerator for rubber according to claim 1, wherein the carboxylic acid is at least one selected from aromatic and aliphatic. 4. A rubber composition comprising chlorosulfonated polyethylene, epichlorohydrin rubber, chlorinated polyethylene, chlorinated butyl rubber, and fluororubber compounded with the compound according to any one of claims 1 to 3. 5. A vulcanized product obtained by vulcanizing the rubber composition according to claim 4.