JPH0721063B2 - Method for manufacturing rubber laminate - Google Patents

Description

The present invention relates to a method for producing a rubber laminate having a fluorine-containing rubber layer. More specifically, the present invention relates to a method for producing a laminate of a rubber layer containing fluororubber as a main component, which is firmly vulcanized and bonded without an intermediate layer or an adhesive, and an elastomer layer other than fluororubber.

[Conventional technology]

In recent years, the demands on the performance of rubber materials have become stricter year by year, and the types of rubber materials used have changed. Among rubbers, fluororubber has outstanding performance compared with other special rubbers in solvent resistance, heat resistance, chemical resistance, and weather resistance, and the demand for it in the industrial products, automobiles, and aircraft fields is increasing year by year. It has increased. However, the price thereof is extremely high as compared with elastomers other than fluororubber, and the specific gravity is high, so that the product price is remarkably increased, so that the fields to be used have been limited. In this way, it can be said that it has become difficult to deal with one kind of rubber material in order to simultaneously satisfy the contradictory requirements of high performance and low price.

To meet such demands, a method of mixing or laminating an elastomer other than fluororubber with fluororubber has been proposed. However, in the former case, it is difficult to obtain a uniform mixed state, and sufficient performance has not been reached. In the case of lamination, strong adhesion to an elastomer other than fluororubber is extremely difficult due to the low surface energy and low reactivity that are the characteristics of fluororubber. Its use as a body was limited.

[Problems to be solved by the invention]

An object of the present invention is to provide a method capable of firmly adhering and laminating with an elastomer other than fluororubber without impairing the excellent performance of the fluororubber.

[Means for solving problems]

That is, the present invention provides (1) at least one compound selected from the hydrochlorides, phenol salts and sulfonates of the compounds (a) and (b) represented by the following general formula. (2) An unvulcanized rubber layer containing at least one compound selected from oxides, hydroxides and carbonates of metals of Groups II to IV of the periodic table and a fluorine-containing unvulcanized rubber layer and / or fluorine. It is intended to provide a method for producing a laminate having a fluorine-containing rubber layer, characterized in that the rubber is contained in an unvulcanized rubber layer and both rubber layers are vulcanized and adhered.

Hereinafter, the present invention will be described in more detail.

The fluororubber used in the unvulcanized rubber layer containing a fluororubber as a main component in the present invention is a fluorinated rubber-like copolymer, and these copolymers include, for example, vinylidene fluoride and other fluorine. It is a copolymer with an olefin containing vinyldenfluoride and hexafluoropropene, pentafluoropropene, trifluoroethylene, trifluorochloroethylene, tetrafluoroethylene, vinylfluoride, perfluoro (methyl vinyl ether), perfluoro ( Examples thereof include a copolymer with at least one kind such as propyl vinylidene). In addition, a vinyl compound, an olefin compound, a diene compound, an α, β-ethylenically unsaturated carboxylic acid, or the like may be copolymerized with these copolymer components.

Among these, vinylidene fluoride-hexafluoropropene binary copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropene ternary copolymer, tetrafluoroethylene-propylene binary copolymer and tetrafluoroethylene-vinylidene Fluoride propylene terpolymers are preferred.

Elastomers other than fluororubber used for the unvulcanized rubber layer containing no fluororubber of the present invention include polybutadiene, styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, natural rubber, polyisoprene, propylene-butadiene copolymer. Polymer, ethylene-propylene copolymer, ethylene-propylene-diene terpolymer, polychloroprene, isobutylene-isoprene copolymer, acrylonitrile-butadiene-styrene terpolymer, polyvinyl chloride, polyvinyl chloride copolymer Coalesce, polyepichlorohydrin rubber, epichlorohydrin copolymer, copolymer of epichlorohydrin with other saturated or unsaturated epoxide, poly-1-chlorobutadiene, 1-
Chlorobutadiene-butadiene copolymer, chlorinated butyl rubber, chlorosulphonated polyethylene, polyvinylidene chloride, vinylidene chloride copolymer, chlorinated polyethylene, chlorinated polypropylene, brominated butyl rubber, polyvinylidene bromide, vinylidene bromide copolymer Examples thereof include coalescing, polyethylene bromide, acrylic rubber, copolymers of acrylic rubber with vinyl compounds, olefin compounds, diene compounds, α, β-ethylenically unsaturated carboxylic acids and the like. Of these, polybutadiene, acrylonitrile-butadiene copolymer, epichlorohydrin-based copolymer, and ethylene-propylene-based copolymer are preferable.

The metal oxides, hydroxides or carbonates of Group II to IV of the periodic table used in the present invention are specifically magnesium oxide, zinc oxide, calcium oxide, calcium hydroxide,
There are calcium carbonate, lead oxide, aluminum hydroxide, silicon dioxide and the like, and one or more of these may be used in combination. Of these, silicon dioxide is preferred.

Used in the present invention, a hydrochloride salt of the compound (a) and / or (b) represented by the general formula, a phenol salt,
Sulfonate, (hereinafter sometimes simply referred to as “salt”), or a hydrochloride of the compound (a) and / or (b) represented by the above general formula, a phenol salt, a mixture with a sulfonate (hereinafter, Sometimes referred to simply as "mixture")
Is.

Here, the compound represented by the general formula (a) means 1,8-diaza-bicyclo (5,4,0) undecene-7 (hereinafter, simply referred to as “D
Sometimes referred to as "BU"), and such a compound may be a ring in which a hydrogen atom is replaced by another atom or molecule.

Further, the compound represented by the general formula (b) is 1,5-diaza-
Bicyclo (4,3,0) nonene-5 (hereinafter may be simply referred to as “DBN”), which is a compound in which a hydrogen atom of a cyclic ring is replaced by another atom or molecule as in the above compound. May be

Examples of the sulfonic acid compound used as the sulfonate include benzenesulfonic acid, dodecylbenzenesulfonic acid, o, m, p-toluenesulfonic acid, 2,4-toluenedisulfonic acid, sulfanilic acid, naphthalenesulfonic acid, naphthoic acid, p -Sulfobenzoic acid, etc. may be mentioned, and these compounds may be those in which the hydrogen atom of the cyclic ring has been replaced by another atom or molecule.

In the case of a mixture, the mixing ratio of the hydrochloride, phenol salt and sulfonate of the general formulas (a) and / or (b) is usually 1/5 to 5/1 (molar ratio).

The amount of each component used is 100 parts by weight of the elastomer in each layer, and the compound (a) and / or (b) represented by the above general formula has a hydrochloric acid salt, a phenolic salt and a sulfonic acid salt of 0.
It is 1 to 10 parts by weight, preferably 0.3 to 5 parts by weight. Preferably, the compound (a) and / or (b) hydrochloride, phenol salt or sulfonate is added to both layers. The amount of the oxides, hydroxides and carbonates of metals of Group II to IV of the periodic table used is 0.1 to 100 parts by weight, preferably 1 to 50 parts by weight per 100 parts by weight of the elastomer.

In the present invention, in the unvulcanized rubber layer containing a fluororubber as a main component, other known auxiliary materials depending on the purpose, such as a crosslinking agent (peroxide compound, polyol compound, dithiol compound, amine compound, etc.), crosslinking promotion An agent, a stabilizer, a colorant, a plasticizer, a reinforcing agent (carbon black or the like), a filler, an antiaging agent, a processing aid and the like may be blended.

Also in the unvulcanized rubber layer containing no fluororubber, similarly known crosslinking agents, crosslinking accelerators, stabilizers, plasticizers, colorants, reinforcing agents, fillers, antioxidants, processing aids, etc. It can be blended.

These blends can be kneaded by an ordinary kneading machine such as a roll or a Banbury mixer, and then molded and vulcanized under ordinary vulcanized rubber production conditions. The vulcanization temperature, vulcanization time, and pressure are not particularly limited, but an unvulcanized rubber layer containing fluororubber as a main component and an unvulcanized rubber layer not containing fluororubber are contacted in an unvulcanized state, Usually 2-100k
A vulcanized laminate is obtained by heating to 100 to 200 ° C. under a pressure of g / cm ² G. It is also possible to shorten the primary vulcanization time and improve the adhesive strength by heat-treating (post-curing) the laminate.

〔Example〕

 Examples 1 to 44 and Comparative Examples 1 to 20 Next, the present invention will be described with reference to Examples.

Fluorine rubber, polybutadiene rubber, acrylonitrile-
Butadiene rubber, polyepichlorohydrin rubber or ethylene-propylene-diene terpolymer was kneaded on a 40 ° C. roll according to Tables 1-5. The unvulcanized 2 mm thick sheets that have been kneaded are brought into contact with each other, press-crosslinked for 20 minutes at 170 ° C., punched out to a width of 1 cm, and then T-shaped according to JIS-K6854-1973.
A mold peeling test was conducted.

The results are shown in Table-6.

As shown in Table-6, it can be seen that the adhesive strength of the table containing DBU-P-toluenesulfonate DBN-P-toluenesulfonate and DBU-phenol salt is remarkably improved.

〔The invention's effect〕

By the method of the present invention, a rubber laminate in which a rubber layer containing fluororubber as a main component and a rubber layer containing no fluororubber are firmly vulcanized and bonded is obtained. Further, the present invention is to make it possible to produce a laminate with an elastomer other than fluororubber while maintaining the heat resistance, oil resistance, chemical resistance and weather resistance which are the characteristics of fluororubber.

Specific applications of the laminate having a fluororubber layer produced by the present invention include various hoses, such as fuel oil hoses, oil hoses, gas hoses, brake oil hoses, industrial parts, automobiles. , Use for parts such as aircraft.

Claims (1)

[Claims] 1. When vulcanizing an unvulcanized rubber layer containing a fluororubber as a main component and an unvulcanized rubber layer containing no fluororubber in superposition, at least one of the layers is vulcanized.
(A) at least one compound selected from the compounds (a) and (b) represented by the following general formula, hydrochlorides, sulfonates, and phenol salts; and (B) a group II-IV group of the periodic table. A method for producing a rubber laminate, comprising blending at least one compound selected from metal oxides, hydroxides and carbonates. Record