JP3526663B2 - Elastomer composition having epoxy group - Google Patents

Description

Description: TECHNICAL FIELD [0001] The present invention relates to an elastomer composition having an epoxy group. More particularly, the present invention relates to an elastomer composition which provides an elastomer vulcanizate having processing safety and improved compression set. As vulcanizing agents for elastomers having epoxy groups, thermally decomposable ammonium salts, metal salts of dithiocarbamic acid, amines and polyamine salts are generally and widely used. However, elastomer vulcanizates using these vulcanizing agents have relatively large compression set, and further improvements are desired. JP-A-63-132925 discloses a vulcanizing composition using an imidazole compound and a urea derivative compound having a urea bond in an elastomer having an epoxy group, but still has insufficient compression set. . SUMMARY OF THE INVENTION The present inventors have developed an elastomer composition having an epoxy group for the purpose of improving the compression set of an elastomer vulcanizate while ensuring processing safety. As a result of various studies on the vulcanization method, an excellent elastomer composition was found, and the present invention was reached. That is, the present invention relates to an elastomer having an epoxy group, an imidazole compound represented by the following general formula (1), isocyanuric acid and N
The present invention relates to an elastomer composition having an epoxy group, which comprises-(cyclohexylthio) phthalimide. Embedded image (In the formula, R ₁ represents an alkyl group having 1 to 17 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, an amino group, a cyano group, or a mercapto group; R ₂ represents a hydrogen atom,
And 17 to 17 represent an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. R ₃ and R _{4 each} represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms or a substituted alkyl group, a cyano group, a hydroxyalkyl group, a carboxyl group, a thiocarbomoyl group, or an imidazolyl group. Hereinafter, the present invention will be described in detail. The elastomer in the present invention is obtained by copolymerizing a monomer having an epoxy group and at least one monomer copolymerizable therewith by a known method such as emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization. Can be The elastomer in the present invention contains 0.1 to 5.0% by weight, preferably 0.5 to 3.0% by weight of a monomer unit having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether or methacryl glycidyl ether as a crosslinking site. It is desirable that they are bound by weight%. The monomers copolymerizable with the monomer having an epoxy group include alkyl acrylates and alkoxyalkyl acrylates as main components, and copolymerizable ethylenically unsaturated compounds as other components. Can be used. Examples of alkyl acrylates include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acrylate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, cyanomethyl acrylate, 1-cyanoethyl acrylate, 2-cyanoethyl acrylate, 1-cyanopropyl acrylate, 2-cyanopropyl acrylate , 3-cyanopropyl acrylate,
4-cyanobutyl acrylate, 6-cyanohexyl acrylate, 2-ethyl-6-cyanohexyl acrylate, 8-cyanooctyl acrylate, and the like. Also included are alkyl acrylates represented by the following general formula (2). Embedded image (Where R ₁ is a hydrogen atom or a methyl group, R ₂ is an alkylene group having 3 to 20 carbon atoms, R ₃ is a hydrocarbon group having 1 to 20 carbon atoms or a derivative thereof, and n is an integer of 1 to 20) Examples of the alkoxyalkyl acrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2- (n-propoxy) ethyl acrylate, 2- (n-butoxy) ethyl acrylate, and 3-methoxyethyl acrylate. Propyl acrylate, 3-ethoxypropyl acrylate, 2- (n-propoxy) propyl acrylate, 2- (n-butoxy) propyl acrylate and the like. As the copolymerizable ethylenically unsaturated compound, various compounds can be used if necessary. Examples thereof include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, and maleic acid. , Fumaric acid, itaconic acid, and other compounds having a carboxyl group;
-Dihydroperfluoroethyl (meth) acrylate,
1,1-dihydroperfluoropropyl (meth) acrylate, 1,1,5-trihydroperfluorohexyl (meth) acrylate, 1,1,2,2-tetrahydroperfluoropropyl (meth) acrylate, 1,1,
7-trihydroperfluoroheptyl (meth) acrylate, 1,1-dihydroperfluorooctyl (meth)
Acrylates, fluorinated acrylates such as 1,1-dihydroperfluorodecyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2
-Hydroxypropyl (meth) acrylate, acrylate having a hydroxyl group such as hydroxyethyl (meth) acrylate, acrylate having a tertiary amino group such as diethylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, Methacrylates such as methyl methacrylate and octyl methacrylate, alkyl vinyl ketones such as methyl vinyl ketone, vinyl and allyl ethers such as vinyl ethyl ether and allyl methyl ether, styrene, α
-Methyl styrene, chlorostyrene, vinyl aromatic compounds such as vinyl toluene, acrylonitrile, vinyl nitrile such as methacrylonitrile, ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, vinyl propionate, Alkyl fumarate and the like. Next, the imidazole compounds in the present invention include 1-methylimidazole, 1,2-dimethylimidazole, 1-methyl-2-ethylimidazole,
1-benzyl-2-ethylimidazole, 1-benzyl-2-ethyl-5-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-phenylimidazole trimellitate, 1-aminoethylimidazole 1-aminoethyl-2-methylimidazole, 1-aminoethyl-2-ethylimidazole,
1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-methylimidazole tri Melitate, 1-cyanoethyl-2-phenylimidazole trimellitate,
1-cyanoethyl-2-ethyl-4-methylimidazole trimellitate, 1-cyanoethyl-2-undecyl-imidazole trimellitate, 2,4-diamino-6
-[2'-methylimidazolyl- (1) '] ethyl-s
-Triazine / isocyanuric acid adduct, 1-cyanoethyl-2-phenyl-4,5-di- (cyanoethoxymethyl) imidazole, N- (2-methylimidazolyl-
1-ethyl) urea, N, N′-bis- (2-methylimidazolyl-1-ethyl) urea, 1- (cyanoethylaminoethyl) -2-methylimidazole, N, N ′-[2
-Methylimidazolyl- (1) -ethyl] -aziboyldiamide, N, N '-[2-methylimidazolyl-
(1) -ethyl] -dodecanedioyl diamide, N,
N '-[2-methylimidazolyl- (1) -ethyl]-
Eicosandioilodiamide, 2,4-diamino-6
[2′-Methylimidazolyl- (1) ′]-ethyl-s
-Triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1) ']-ethyl-s-triazine, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1,3- Dibenzyl-2-methylimidazolium chloride and the like. The amount of these additives is preferably from 0.2 to 5.0 parts by weight, more preferably from 0.5 to 3.0 parts by weight, and preferably less than 0.2 parts by weight, based on 100 parts by weight of the elastomer. Then, the physical properties of the elastomer vulcanizate are not enough,
If the amount exceeds 5.0 parts by weight, processing safety may be impaired. The amount of each of isocyanuric acid and N- (cyclohexylthio) phthalimide to be added is preferably 0.1 to 5.0 parts by weight, more preferably 0.3 to 4.0 parts by weight, based on 100 parts by weight of the elastomer. Parts are more preferred. 0.
If the amount is less than 1 part by weight, the vulcanization rate and the compression set are not sufficiently improved. If the amount exceeds 5.0 parts by weight, there is a possibility that a problem may occur in molding. In the present invention, for the purpose of adjusting the vulcanization rate, a curing agent for an epoxy resin such as a pyrolytic ammonium salt, an organic acid, an acid anhydride, an amine, sulfur and a sulfur compound is further used in the present invention. The effect can be added as long as the effect is not reduced. Further, when the elastomer composition of the present invention is put to practical use, a reinforcing agent, a filler, a plasticizer and the like are added to the elastomer composition, followed by molding and vulcanization. A corresponding elastomer vulcanizate can be obtained. The kneading and vulcanization of the elastomer composition of the present invention can be carried out by a method commonly used in the rubber industry. The elastomer vulcanizate obtained from the elastomer composition of the present invention is excellent in heat resistance, oil resistance and severe durability, and is suitable for industrial parts such as belts, hoses, oil seals, gaskets and diaphragms. In particular, it can be expected to improve the reliability as a part for an automobile, which has strict quality requirements. EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 4 and Comparative Examples 1 to 8 In a polymerization vessel, 40 kg of a mixed solution of 10 kg of vinyl acetate and 30 kg of n-butyl acrylate, 43 kg of a 4% by weight aqueous solution of partially saponified polyvinyl alcohol, and sodium acetate 60
0 g and glycidyl methacrylate (600 g) were charged and mixed well with a stirrer in advance to prepare a uniform suspension. After the inside of the polymerization vessel was replaced with nitrogen gas, ethylene monomer was injected from above, and the pressure was adjusted to 50 kg / cm ² at a polymerization temperature of 45 ° C. Subsequently, a polymerization initiator aqueous solution was separately added from an injection port, and polymerization was performed for about 10 hours. After 12 hours, unreacted monomers in the polymer emulsion produced are removed, and a 3% by weight aqueous solution of borax is added to coagulate the emulsion, followed by washing, dehydration, 120-1
After drying on a roll at 30 ° C. for 20 minutes, a sheet-like raw rubber was obtained and subjected to a test. Next, according to the formulation shown in Table 1, kneading was carried out using a 6-inch roll to produce a 2.3 mm thick sheet, and this sheet was press-vulcanized at 170 ° C. ×
After performing for 20 minutes, 160 ° C in a gear oven
After vulcanization for 4 hours, a test piece for evaluating the physical properties of the elastomer vulcanizate was prepared. JIS K for physical properties test of vulcanizates
6301, and Mooney Scoach is JIS
The measurement was performed according to K6300, and the results are shown in Table 2. [Table 1] [Table 2] The elastomer composition having an epoxy group of the present invention is excellent in processing safety, as is apparent from the examples, and particularly, the high temperature compression set of the elastomer vulcanizate is improved. .

Continuation of front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 63/00-63/10 C08G 59/40

Claims (1)

(57) [Claim 1] An elastomer having an epoxy group, an imidazole compound represented by the following general formula (1), and isocyanuric acid and N- (cyclohexylthio) phthalimide. An elastomer composition having an epoxy group, characterized by comprising: Embedded image (In the formula, R ₁ represents an alkyl group having 1 to 17 carbon atoms, a substituted alkyl group, an aryl group, a substituted aryl group, an amino group, a cyano group, or a mercapto group; R ₂ represents a hydrogen atom,
And 17 to 17 represent an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group. R ₃ and R _{4 each} represent a hydrogen atom, an alkyl group having 1 to 17 carbon atoms or a substituted alkyl group, a cyano group, a hydroxyalkyl group, a carboxyl group, a thiocarbomoyl group, or an imidazolyl group. )