JP3288486B2 - Elastomer composition having epoxy group - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a vulcanizate of an elastomer having an epoxy group. More specifically, it relates to an elastomer vulcanizate having high-speed vulcanizability and processing safety, and having improved compression set.

[0002]

2. Description of the Related Art As a vulcanizing agent for an elastomer having an epoxy group, a thermally decomposable ammonium salt, a metal salt of dithiocarbamic acid, an amine, a polyamine salt and the like are generally widely used. However, vulcanizates of elastomers using these vulcanizing agents have relatively large compression set, and further improvements are desired. In the process of manufacturing an elastomer component, high-speed vulcanization for shortening the vulcanization time is demanded from the viewpoint of improving productivity and saving energy.

Japanese Patent Application Laid-Open No. 63-132925 discloses a vulcanization composition using an imidazole compound and a urea derivative compound having a urea bond as an epoxy group-containing elastomer, and Japanese Patent Application Laid-Open No. 63-57628. Discloses a vulcanizable elastomer composition using an organic compound having two or more bonds represented by the following general formula (3) and a quaternary ammonium salt in an epoxy group-containing elastomer. Not enough in permanent set and vulcanization rate.

Embedded image (X and Y in the formula both represent an oxygen atom or a sulfur atom, or one represents an oxygen atom and the other represents a sulfur atom.)

[0004]

DISCLOSURE OF THE INVENTION The present inventors have developed a method for vulcanizing an epoxy-containing elastomer composition, particularly for the purpose of improving compression set while ensuring high-speed vulcanizability and processing safety. As a result of various investigations, the present invention has been achieved.

[0005]

That is, the present invention relates to an imidazole compound represented by the following general formula (1): 100 parts by weight of an elastomer having an epoxy group.
0 parts by weight, 0.1 to 5.0 parts by weight of an organic compound having two or more partial structural formulas represented by the following formula (2), and 0.1 to 5.0 parts by weight of a quaternary ammonium salt. It is an elastomer composition having an epoxy group, characterized by being contained.

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, and R ₂ represents a hydrogen atom, a carbon atom having 1 carbon atom.
To 17 to 17 represent alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups. 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. )

Embedded image

Hereinafter, the present invention will be described in detail. The elastomer according to the present invention contains 0.1 to 5.0% by weight of a monomer having an epoxy group such as glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, or methacryl glycidyl ether as a crosslinking site,
Preferably, the copolymer is 0.5 to 3% by weight.

The monomer copolymerizable with a monomer having an epoxy group includes an ethylenically unsaturated compound having alkyl acrylate or alkoxyalkyl acrylate as a main component and copolymerizable as other components.

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.

Further, an alkyl acrylate represented by the following general formula (4) is also included.

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-methoxypropyl 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 as required. Examples thereof include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, and maleic acid. Carboxy compounds such as, fumaric acid, itaconic acid, 1,1-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
Fluorinated acrylates such as dihydroperfluorooctyl (meth) acrylate, 1,1-dihydroperfluorodecyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxyethyl (meth) A) hydroxyacrylates such as acrylates; tertiary aminoacrylates such as diethylaminoethyl (meth) acrylate and dibutylaminoethyl (meth) acrylate; methacrylates such as methyl methacrylate and octyl methacrylate; and alkyl vinyls such as methyl vinyl ketone. Ketones, vinyl and allyl ethers such as vinyl ethyl ether and allyl methyl ether, styrene, α-methylstyrene, chlorostyrene, vinyl toluene Vinyl aromatic compounds such as,
Examples include vinyl nitriles such as acrylonitrile and methacrylonitrile, ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl acetate, vinyl propionate, and alkyl fumarate.

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-methyl Imidazole trimellitate, 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]-
Eicosandioildiamide, 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, and more preferably from 0.2 to 5.0 parts by weight based on 100 parts by weight of the elastomer.
If the amount is less than 2 parts by weight, the physical properties of the vulcanized product are not sufficient, and
If the amount is more than the weight part, processing safety may be impaired.

[0014] The following in the molecule of the present invention wherein the multi heterocyclic compounds that the partial structural formula Yusuke two or more of the formula (2)
Two or more include the case where the bonds are apart from each other and the case where the bonds are adjacent to each other. Further, the bond may be exocyclic as a substituent on the heterocyclic compound.

Embedded image Equation (2)

Examples of the heterocyclic compound include parabanic acid, alloic acid, alloxanthin, alloxan-5-oxime,
Barbituric acid, 5-hydroxybarbituric acid, 5-benzalbarbituric acid, 5-aminobarbituric acid, 5-hydroxyiminobarbituric acid, 5,5-diethylbarbituric acid, 5-ethyl-5-phenylbarbit Tulic acid (barbital), 5- (1-methylbutyl) -5- (allyl)
Barbituric acid, 5,5-diallyl barbituric acid, isocyanuric acid, pseudouric acid and the like can be mentioned.

[0016]

[0017]

The amount of these additives is preferably 0.1 to 5.0 parts by weight, and more preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the elastomer.
If the amount is less than 1 part by weight, the vulcanization rate and the compression set are not sufficiently improved, and if the amount exceeds 5.0 parts by weight, there is a possibility that a problem may occur in the moldability.

As the quaternary ammonium salt in the present invention, those represented by the following general formula (5) are used.

Embedded image (Wherein R _{1 to} R ₄ are an alkyl group having 1 to 25 carbon atoms, an alkoxy group, an aryl group, an alkylaryl group, an aralkyl group or a polyoxyalkylene group, and two or three of these groups have a heterocyclic structure. X is a halogen atom anion, such as Cl, Br, or I.)

Examples of quaternary ammonium salts include tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide, cetyltrimethylammonium bromide, n-dodecyltrimethylammonium bromide, and cetyldimethylbenzylammonium chloride. , Methylcetyldibenzylammonium bromide, cetyldimethylethylammonium bromide, octadecyltrimethylammonium bromide, cetylpyridium chloride, cetylpyridiumbromide, 1,8-diaza-bicyclo (5,4,
0) Undecene-7-benzylammonium chloride, cetylpyridium iodide and the like.

The amount of these additives is preferably 0.1 to 5.0 parts by weight, and more preferably 0.1 to 5.0 parts by weight based on 100 parts by weight of the elastomer.
If it is less than 1 part by weight, the vulcanization rate and compression set are not sufficiently improved, and if it exceeds 5.0 parts by weight, processing stability may be impaired.

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 vulcanized elastomer of the present invention is put to practical use, it is molded and vulcanized by adding a reinforcing agent, a filler, a plasticizer, etc. to the elastomer composition according to the purpose. be able to.

The kneading and vulcanization of the elastomer composition in the present invention can be carried out by a method commonly used in the rubber industry.

Since the elastomer composition of the present invention is excellent in heat resistance, oil resistance and severe durability, it is suitable for industrial parts such as belts, hoses, oil seals, gaskets, and diaphragms, and in particular, automobiles for which quality assurance is strict. The reliability can be expected to be improved as parts for use.

[0026]

The present invention will be described below in detail with reference to examples. EXAMPLE In a polymerization vessel, 40 kg of a mixture 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 60 kg of sodium acetate
0 g and glycidyl methacrylate (600 g) were charged, and mixed well with a stirrer in advance to prepare a uniform suspension. After replacing the inside of the polymerization vessel with nitrogen gas, an ethylene monomer was injected under pressure 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.

Subsequently, unreacted monomers in the produced polymer emulsion are removed, and a 3% by weight borax aqueous solution is added to coagulate the emulsion, washing, dehydration and drying (120 to 13).
(20 minutes on a roll at 0 ° C.) to obtain a sheet-like elastomer having epoxy groups.

Next, according to the compounding recipe shown in Table 1, kneading was carried out using a 6-inch roll to produce a sheet having a thickness of 2.3 mm, and this sheet was subjected to press vulcanization at 170 ° C. ×
After 20 minutes, a test piece for evaluating the properties of the elastomer vulcanizate was prepared. The physical property test was performed according to JIS K6301, and the results are shown in Table 2.

[0029]

[Table 1] (Note) 1) Anti-aging agent manufactured by Uniroyal 2) Seast # 116 manufactured by Tokai Carbon

[0030]

[Table 2]

[0031]

As is clear from the examples, the elastomer composition having an epoxy group of the present invention has a high vulcanization rate and an improved compression set.

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-132925 (JP, A) JP-A-2-20516 (JP, A) JP-A-63-57628 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) C08G 59/40 C08G 59/50-59/60 C08L 63/00-63/10

Claims (1)

(57) [Claims] 1. An elastomer 100 having an epoxy group
Parts by weight, 0.2 to 5.0 parts by weight of an imidazole compound represented by the following general formula (1), and a heterocyclic organic compound having two or more partial structural formulas represented by the following formula (2) 0.
1 to 5.0 parts by weight, and quaternary ammonium salt 0.1
An elastomer composition having an epoxy group, wherein the elastomer composition comprises about 5.0 parts by weight. Embedded image Formula (1) (wherein 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, and R ₂ represents a hydrogen atom, a carbon atom Number 1
To 17 to 17 represent alkyl groups, substituted alkyl groups, aryl groups, and substituted aryl groups. 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. Equation (2)