DE1494002B1 - Process for joining plastics, leather, textiles or elastomers with natural or synthetic elastomers - Google Patents

Description

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It is known to achieve a vulcanized solution or a latex of the copolymer one-binding layers between materials that are normally coated, pressed and then vulcanized, are difficult to combine, synthetic Here, the polymers of butadiene and acrylonitrile usually used for vulcanization come which contain a proportion of methacrylic acid that is dependent on natural or synthetic elastomers, the vulcanization temperatures to be used are preferred. The connection takes place at least at temperatures between 110 to 180 ^° C., partly via the carboxyl groups of the methacrylic group, the vulcanization times depending on the acid, which react with metal oxides (e.g. zinc oxide) to form the type or thickness of the materials to be connected capital. Connections between buta directives. If, for example, the acrylonitrile copolymers and chlorobutaio binding of shoe uppers and rubber soles are concerned, then diene polymers can be produced in this way after the generally sufficient vulcanization times between German Auslegeschrift 1,034,297. 2 and 25 minutes.

Polymers of this type are also suitable for emulsions

Bonding of films made of polyvinyl chloride with paper known latex auxiliaries both lower and

or other permeable materials. A mixture of high molecular weight, for example polyvinyl

binding of polyvinyl chloride with rubber or with alcohol or casein can be added to the viscous

Polyvinyl chloride itself, however, is done in this way, the stability, the drying time, the flow or

not possible. also to influence the properties for leather finishing

It is also known that natural rubber flows.

and natural rubber latex have adhesive properties, 20 The additional use of organic which in several respects from the synthetic isocyanate releasers, d. H. of connections made in Polymers are not achieved. The user can set free NCO groups and the "Duhgsberelch für natural rubber" is nevertheless - for example - from polyvalent isocyanates and phenols limited to this, since its effects are very often available in the, also brings in a majority Cases fail in which polar substances, -z. B. Butadiene- 25 of cases a further improvement with it. Next styrene, Both the emulsions and the butadiene-acrylonitrile or vinyl chloride-poly can be used merisate, with non-polar substances, such as natural chewing solutions with vulcanizing agents, such as sulfur, Tschuk or butadiene homopolymers are connected to sulfur-donating substances, tetramethylthiuram should. disulfide, zinc oxide and accelerators or organi-There has now been a process for connecting 30 peroxides, polyisocyanates and aging plastics Leather, textiles, natural or syn- protective agents, plasticizers and fillers aesthetic Elastomers or their vulcanizates are used. With the copolymers mentioned Vulcanisable, natural or synthetic, grained leather, prepared (not Elastomers using copolymers) leather, polyvinyl chloride, textiles, as a binder and followed by Vülkanisa- 35 natural and synthetic rubbers with natural and tion found, which is characterized in that synthetic rubbers stick together as well as zuman Vulcanize emulsion copolymers as a binder. That is of particular importance aliphatic conjugated diolefins with no more processes for the direct vulcanization of mials 8 carbon atoms and methyl esters of acrylic mixtures from natural and synthetic masticatory acid and / or methacrylic acid used, at 40 chuk on shoe uppers made of leather or plastic. Copolymerization the total amount of diolefin even mixtures of oil-extended butadiene-styrene component initially with 40 to 60 percent by weight rubbers that contain up to 50% oil the total amount of the acrylate mono to be used is vulcanized onto shoe uppers. It is sufficient meren up to 40 to 70% polymerized and then in the former case, the leather or the rubber with ßend after adding the remaining amount of the acrylate 45 to coat the latex or the solution to a monomeric, either continuously or staggered, complete binding during a subsequent or in one portion, has been polymerized. bring about vulcanization. Technically Among natural or synthetic elastomers, the HiKe of these binders is also important Here are natural rubber or synthetic rubbers made possible production of laminates from of various types, for example based on 50 natural rubber or synthetic rubber mixtures Butadiene, isoprene or chloroprene homo- or with plastics. The procedure is quite general -Mixed polymers with a wide variety of copoly- valuable in those cases in which the merisable components, for example acrylic vulcanisation of cover or intermediate layers nitrile or styrene, or stereospecific diene polymer from natural or synthetic rubber hansate, and also special products such as Siliconkaur 55 delt, d. H. to parts that do without the help of special to understand chuke. ·. ■ · -. - Adhesive solutions or application of special measures for the method according to the invention are taken as difficult to connect, for example Adhesion promoter copolymers made from butadiene (1,3), in the manufacture of car mats, where one 2-methylbutadiene, 2-chlorobutadiene or 2,3-dime - relatively cheap rubber underlayer on a mostly gethylbutadiene and methyl methacrylate, a colored layer of plastics, for example polyester used. vinyl chloride, can be vulcanized into the polymer to be used according to the invention by the claimed process. Similarly, the sowing the proportion of acrylic acid or methacrylic production of floor coverings possible, with z. B. acid esters vary between 10 and 90%. oil-resistant, polar synthetic rubbers (butadiene-esp favorable effects are achieved with a content of 65 acrylonitrile or chloroprene polymers) or between 40 and 70% achieved. Plastics (polyvinyl chloride) on a cheap sub-Zur Achievement of particularly high adhesive strengths. Sheet made from rubber mixtures with a high content of regenerate the parts to be connected are either vulcanized on with a gene.

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Another area of application relates to tearing elements and no separation in the connection of medical adhesive strips with a plastic layer. If the same test carrier films, for example based on vinyl chloride order, are adhered to using a copoly-polymer. Here, the adhesion of the natural merizates, consisting of 50% butadiene and 50% rubber adhesive layer on the carrier film, is considerably 5 styrene, so there is no adhesion whatsoever.
improved. b) Will normally finished leather, which does not have any

The parts mentioned below are Ge casein finish, at the junction with

parts by weight, unless otherwise noted: the latex or the solution of the above

_TT . ", ■ _. . . Coated copolymer and after drying

Production of the copolymers _J? ^ f ^ Mixture of natural or synthetic

A. The following are placed in an autoclave: 184 parts of chuk are vulcanized together to form bonds Water, 3.4 parts of the potassium salt of the disproportionate, which is sufficient for many cases of practice renated abietic acid, but 0.4 parts trisodium phosphate are lower than those achieved by method a), and 0.3 part of tetraethylene pentamine. Then c) is used in the dressing of the leather closed, the autoclave evacuated and the vacuum 15 instead of the usual leather ties the latex according to balanced with nitrogen. Thereupon 0.1 parts of procedure A are carried out without further pretreatment mixed tertiary long-chain mercaptans, 23 parts of the leather when vulcanized together with mixed methyl methacrylate and 50 parts of butadiene injected, excellent genes made from natural or synthetic rubber the autoclave is cooled to 5 ° C, and adhesions are achieved at 5 ° C. During the tensile test, the pressed 0.3 parts cumene hydroperoxide in 2 parts 20 separation in leather or in rubber, but not in the Dissolved methyl methacrylate. With a conversion of 17 g of bonding layer.

the remaining 25 parts of methyl methacrylate are added.

filled. The batch is carried out with a yield of up to 34 g. Example 2

drive with 1.5% bis-CS-cyclohexyl-S-methyl ^ -oxy- " _too vulcanization of polyvinyl chloride '

phenylj-methane stabilized and then degassed. 25 ^ _t rubber

The latex obtained in this way can be alkaline with an

saline solution provided. a) Films made of polyvinyl chloride are with the

B. Another possibility of the latex copolymerization or the solution of the copolymer, according to butadiene and methyl methacrylate, is the following: Process A prepared, painted. After 175 parts of water, 3.4 parts of isomerized abietin-3 ° drying, a vulcanizable rubber acid potassium, 0.4 part of trisodium phosphate and a mixture is applied and both parts together are a solution of 9.1 parts of water and 0.1 part of sodium - vulcanized. During vulcanization, a salt of ethylenediaminetetraacetic acid is formed, 0.24 parts of an intimate combination of the two elements. The strength of normal sulfuric acid, 0.003 parts of ferrous sulfate and the speed of the adhesive layer is higher than the structural strength of 0.12 parts of formaldehyde sodium sulfoxylate. The same is placed in the autoclave, the autoclave is closed, the result is obtained when instead of the plastic, the vacuum is evacuated and the vacuum is equalized with nitrogen. film the rubber layer is coated.
Then 0.1 part of mixed tertiary mercap b) For the production of shoes, the tane (C ₁₀ -C ₁₄ ), 23 parts of methyl methacrylate and 50 parts of shoe upper made of polyvinyl chloride synthetic leather are pressed in on the butadiene, the autoclave to 5 ° C 40 point where it cools to be connected to the rubber sole and at 5 ° C a solution of 0.14 parts of cumene is added to the latex or the solution of the copolymer hydroperoxide in 2 parts of methyl methacrylate, produced according to method A, streaked and give. With a yield of 17 g, after drying with the rubber mixture, the remaining 25 parts of methyl methacrylate are added. The approach vulcanized together. A perfect yield is achieved with up to 34 g yield, with 1.5% bis-45 tung.

(3-cyclohexyl-5-methyl-2-oxyphenyl) -methane stabili- c) is used in place of the polyvinyl chloride

and then degassed. The latex film obtained in this way is an aqueous dispersion, either the

can with an alkaline saline solution rubber mixture with the above latex or

be felled. the solution and the polyvinyl chloride

Example 5 <> Dispersion sprayed on or painted on or else

r, ". _x . τ jj the above-mentioned latex added to the dispersion

Vulcanization of leather and _this * _{mixture onto the} rubber mixture

Brought chew. During vulcanization, the polyvinyl

a) The trimmed leather is in the place where chloride and unites at the same time with the

it is to be united with the rubber by 55 rubber.

Abrasion freed from the dressing and thereby d) From the precipitated, washed and dried

roughened at the same time. The roughened area is Neten copolymer, which is made according to method B

was obtained with the latex or the solution of the copolymer, a mixture according to the following

made from butadiene and methyl methacrylate, manufactured according to the recipe:
Method A, stroked. After drying it turns 60

a vulcanizable mixture of natural or copolymer 100.0

Synthetic rubber applied and under pressure in the zinc oxide active 15.0

Press or vulcanized in the autoclave, whereby it is far- benzoic acid 2.0

going is independent whether an unfilled or filled sulfur 2.5

Mixture is used. The vulcanization takes place 65 2-mercaptobenzothiazole 1,2

a compound of leather with rubber of so diphenylguanidine 0.5

high separation strength, that in the tensile test tetramethylthiuram monosulfide 0.5

the weaker material of the associated rosin 3.0

Claims (1)

5 6 Kaolin 60.0 schung applied, and both parts are precipitated together Silicic acid 30.0 vulcanized. A separation strength is achieved that Mineral oil 2.0 is above the structural strength of the vulcanizates. Mineral rubber 3.0 _. Anti-aging agent 1,2 5 claim: Phenylbetanaphthylamine Process for joining plastics, Iron oxide red 4.0 leather, textiles, natural or synthetic Elastomers or their vulcanizates with vulcanized If this mixture comes into contact with natural or synthetic elastomer materials that can be vulcanized from polyvinyl chloride, an intimate io meren using copolymers as Association achieved, the adhesive strength of which is greater, binders and then vulcanized than the structural strength of the rubber. sation, characterized in that emulsion copolymers are selected as binders Example 3 aliphatic conjugated diolefins with not Connections of mixtures ¹ S ™ ^or _A ^aIs , ⁸ . Carbon atoms and methyl esters made of butadiene-acrylonitrile rubber with vulcanizates f ^{T use} acrylic acid and / or methacrylic acid of the same rubber det, when they are copolymerized the total amount of the diolefin component initially with 40 to 60 The vulcanizate of a mixture of butadiene weight percent of the total amount to be used Acrylonitrile rubber is polymerized up to 40 to 70% at the junction of 20 acrylate monomers carefully cleaned of mold paint and then after adding the remaining amount with the solution of the copolymer, which after the acrylate monomer, either continuously Method A or B was produced, deleted. or staggered ^ or in one portion, from poly- After drying, an unvulcanized Mimerized.