DE1694073A1 - Use of organosilicon compounds as swim skin prevention agents in the manufacture of dipping articles using the latex dipping process - Google Patents

Description

FARBENFABRIKEN BAYER AG _T6 g ₄ o73 LEVERKU S EN-Bayerwerk

petent-AbteUunf 1, September 1966 Hb / Ru

Use of organosilicon compounds as

Web contraceptives in the manufacture of

Dipping articles after the latex dipping process

Thin-walled rubber articles are made according to known methods by dipping a wooden, glass * porcelain or metal mold Made in natural or synthetic rubber latex, this is where the low surface tension makes it Latices are noticeable to the extent that films of uneven wall thickness are formed on the molds. Especially with the In the manufacture of gloves, this effect is shown to a greater extent. When pulling the mold out of the liquid Latex forms a thin, liquid form between the fingers Latex membrane that only bursts when the tips of the fingers leave the latex surface (so-called web formation). The latex flows off more strongly in this webbing than in the remaining mold wall. As a result, it occurs between the fingers at the attachment points of the web on the mold a reduction in the amount of latex adhering to the mold and thus a reduction in the wall thickness of the dried-on material Latex films at this point.

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It is known that by adding oil or fat emulsions to the latices due to the effect of increasing the surface tension this webbing can be prevented, however, the effect is only limited (about 1-2 days), since the oil or fat dissolves in the rubber and thus out of the water Phase is eliminated and becomes ineffective.

It is also known to add organosilicon compounds to the latex, which are stirred into the latex as an aqueous emulsion or as a colloidal solution. The organosilicon compounds that have become known for this purpose have different structures and molecular sizes. In addition to hydrophobic polysiloxanes, particularly high molecular weight organosilicon compounds are used which contain grafted-on alkylene oxide chains. In addition to the hydrophobic organosilicon segments, these compounds contain hydrophilic groups in the molecule and also have emulsifying properties. Combinations of water-soluble compounds with hydrophobic polysiloxanes, which are added to the latex as emulsions, have also become known. In these emulsions, the _E hydrophilic, water-soluble polysiloxane has the function of an emulsifier.

It has now been found that with emulsifier-free emulsions of polysiloxanes that carry anionic salt groups that can prevent webbing without causing a streak-shaped course of the latex comes. These polysiloxanes

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3. 169A073

are built up like block polymers, their organopolysiloxane blocks by isocyanate addition with anionic Groups bearing segments are connected. One receives on this way polysiloxanes, the hydrophobic character of which is different depending on the composition and which have hydrophilic centers due to the presence of the salt-like groups, which enable the production of aqueous emulsions including colloid-disperse solutions without the addition of Allow emulsifiers or dispersion auxiliaries. The emulsions are well compatible with natural and synthetic latex.

It'll be with these new webbing contraceptives Get diving articles of uniform wall thickness. Uneven Places and especially places of low wall thickness do not occur. Because of the good compatibility of the anionic Polysiloxanes with latex, the appearance of so-called fish eyes in the running latex film is also not observed, which are caused by demulsified oil droplets

can.

The invention therefore relates to the use of organosilicon compounds as webbing preventive agents in the manufacture of dipped articles using the latex dipping process from natural or synthetic latex. The invention is characterized in that as organosilicon compounds higher molecular weight, anionic salt groups carrying polysiloxanes are used, which after the isocyanate

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Polyaddition process from polysiloxanes with reactive hydrogen atoms with a molecular weight of 600 - 4000, preferably 800-2000, polyisocyanates and a compound with at least one amino group with at least one with Isocyanate groups reacting hydrogen atom and at least a carboxylate and / or sulfonate group and optionally low molecular weight chain extenders with reactive Hydrogen atoms have been obtained.

To prevent webbing, it is advisable to add 0.05-10%, preferably 0.1-2 %, of the anionic polysiloxane as an aqueous, emulsifier-free emulsion to the latex.

To achieve sufficient effectiveness in the immersion process, the anionic poly-, siloxanes containing salt-like groups to be used according to the invention as swim skin preventives can preferably be 20 - 85 # polysiloxane structural components with reactive hydrogen atoms and expediently 0.1 - J>%, preferably 0.5 - 1.5 % t contain carboxylate and / or sulfonate groups, these groups being defined as follows:

As a starting component for the preparation of the salt-like groups containing anionischem.Polysiloxane are for example the following! Connections suitable? Polysiloxanes with reactive hydrogen atoms.

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BATH ORIGINAL

The polysiloxanes with reactive polysiloxanes which are used as starting material for the swim skin contraceptives according to the invention Hydrogen atoms obey the general sum formula

^R n ^Si0 4-n ■ - ·

In this formula, at least one H is a carbofunctional organic radical and all the rest of R are optionally indifferently substituted aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, preferably methyl or phenyl groups, while η has a value of more than 1 and at most 2. The carbofunctional organic radical can generally have the grouping - '- -

-R ¹ -Y

are awarded, where R ^{r is} a divalent aliphatic hydrocarbon radical with 1 to 6 carbon atoms, which can be interrupted by ether or thioether groups, and Y is preferably a hydroxyl group *

Suitable carbofunctional radicals are, for example:

Hydroxymethyl

Hydroxybutyl ^

P-hydroxyethyl-oxymethyl-CHg-O-CHg-CHg-OH

^ 3-Hydroxyethyl-mercaptomethyl-CHg-S-CHg-CHg-OH

/ ^, y-dihydroxypropyl-mercaptomethyl -CHg-S-CHg-CHOH-CHgOH

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These organopolysiloxanes slnd ₌ accessible by several known methods. For example, the hydroxymethylpolysiloxanes can be prepared by direct reaction of bromomethylpolysiloxanes with alcoholic potassium hydroxide solution.

In many cases, the functional groups are attached first introduced low molecular weight siloxanes; those won in this way Products are then subjected to the well-known equilibration reactions converted into higher molecular weight polysiloxanes.

Polysiloxanes with a molecular weight of 600-4000 and especially between 800-2000. Also preferred are essentially linear polysiloxanes with terminal ends Hydroxyl groups.

All diisocyanates are suitable as polyisocyanates, such as. B. ^, V-biphenylmethane ^{diisocyanate, 4.4 f} -diphenyldimethylmethane diisocyanate Dl- and tetraalkyldiphenylmethane diisocyanate Κ 4.4 ^I -dibenzyl diisocyanate, 1,5-phenylene diisocyanate, 1,4-phenylene diisocyanate, the isomers of tolylene diisocyanate, optionally in a mixture. Aliphatic diisocyanates are preferred. such as butane-1,4-diisocyanate, hexane-tjö-diisocyanate, dioyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate.

To those used in the production of the anti-seizure contraceptives according to the invention optionally also to be used chain extenders known per se with reactive ones Hydrogen atoms count: '

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1. the usual saturated and unsaturated glycols like Ethylene glycol or condensates of ethylene glycol, butanediol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, hexanediol, Bis-hydroxymethylcyclohexane, Dioxäthyldianj

2. the aliphatic, eycloaliphatic and aromatic Diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexylenediamine, Benzidine, diaminodiphenylmethane, the isomers

des phenylenediamines; M.

3. Amino alcohols such as ethanolamine, propanolamine, butanolamine;

4. Water.

As compounds with at least one amino group with at least a hydrogen atom reacting with isocyanate groups and at least one carboxylate and / or sulfonate group if necessary mixed in embossing:

1. the alkali salts of aliphatic, eycloaliphatic, aromatic and heterocyclic mono- and diaminocarboxylic acids such as glycine, ot- and ^ -alanine, 6-aminoeapronic acid, 4-aminobutyric acid, isomeric mono- and diaminobenaoic acids, lysine, ornithine, the Addition products of acrylic acid and methacrylic acid (in the form of their alkali salts) with diamines such as ethylene diamine and hexamethylene diamine;

2 «the alkali salts of aliphatic and aromatic aminosulfonic acids such as sulfanilic acid, N-phenylamino-methanesulfonic acid, taurine, methylteiarine, butyltaurine, 3-ainotoluene

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N-methanesulfonic acid, 4,4 * -diaminodiphenylether-sulfonic acid (2), 2-aminoanisole-N-methanesulfonic acid, 2, ^ - diaminobenzenesulfonic acid, preferably the addition products of sultones such as propane sultoh or butane sultone to diamines such as ethylenediamine and hexamethylenediamine.

The reaction of the polysiloxanes with reactive hydrogen atoms takes place in the presence or in the absence of solvents. 150 ⁰ CEin pre-adduct prepared, which is then optionally in solution with the optionally used Kettenverlfingerungsmittel and optionally in an organic 'solvent or in water or in mixtures of two - in aligemeinen is first made of the polysiloxane and the polyisocyanate with or without solvent at preferably O dissolved compounds having at least one Aroinogruppe with at least one isocyanate-reacting with hydrogen atom and at least one carboxylate and / or SuIfonatgruppe preferably at 0 - 150 ⁰ C is further reacted..

The molar ratio of isocyanate groups to the total number of all reactive hydrogen atoms is generally between 0.8: 1 and 1.6: 1,,

The implementation is optionally carried out with the use of Solvents carried out »being low-boiling solvents such as acetone, tert. Butanol, HethyISthy! Ketone, Tetrahydrofuran,

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Methylene chloride and benzene are preferably suitable. As a solvent for the compound having at least one amino group with at least one hydrogen atom which reacts with isocyanate groups and at least one carboxylate and / or The sulfonate group can be water or low-boiling alcohols be used. The predominantly linear * High molecular weight, anionic polysiloxanes are converted into the aqueous phase by adding water and the organic phase Solvent removed simultaneously or subsequently. Man receives stable emulsifier-free emulsions that are directly used for Can be used to prevent webbing.

A method for the production of all anti-fungal skin contraceptives according to the invention Compounds to be used are, for example, in the German Aualegeschrif t,,. '. ...... (Patent application F 46 173 IVd / 39c).

In addition to preventing webbing, the agents are distinguished by the fact that they have a favorable effect on the grip properties of the finished article and give them a soft oriff. The surface of the finished article is given a silky sheen. Furthermore, the polysiloxanes used are distinguished by a release effect, so that the vulcanized articles can be detached from the mold more easily. They also have the effect that no disturbing latex skin forms on the surface of the dip tank between the individual dipping processes.

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Particularly suitable as web contraceptives Anionic polysiloxanes are, for example, as follows Polyaddition product

A. Polyaddition product of 236.5 g of the hydroxyl endgroup-containing. carbofunctional polysiloxane the average formula

with an OH content of 2.7 % * 13 ^ * 0 g 1,6-hexane diisocyanate, 52.0 g neopentyl glycol and a mixture of 3 * 8 g xthylenediaroin, 7.6 g 1,3-PrQpansulton and 35 g 10 # Aqueous potassium hydroxide solution in 50 ml of water. .

B. Polyaddition product of 31 ^ * 8 g of the above polysiloxane with an OH content of 2.7 %, 82.0 g of 1,6-hexane diisocyanate and a mixture of 7.52 g of ethylenediamine, 15 * 26 g of 1.3- Propane sultone and 50 g of 10% aqueous sodium hydroxide solution in 50 ml of water.

C. Polyaddition product of 157% of the above polysiloxane with an OH content of 2.7 % * 51 * 0 g 1,6-hexane diisocyanate and 27 * 8 g lysine sodium.

The above compounds can be made more generally according to the following Regulation to be made:

The higher molecular weight polysiloxane with reactive hydrogen atoms is at 12O ⁰ C for four hours with the diisocyanate and with the chain use that may be used.

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extension funds implemented. After cooling the adduct to 55-60 ° C., the melt is treated with acetone or tetrahydrofuran recorded. If appropriate, it can also be used during the addition of any chain extenders to be used Solvents are added. Then the adduct solution with the compound having at least one amino group with at least one hydrogen atom which reacts with isocyanate groups and at least one carboxylate and / or sulfonate group reacted in aqueous solution. After the Water is added to the reaction and the solvent is distilled off in vacuo. The anionic polysiloxane obtained as an emulsion can be used directly as a web contraceptive in the latex dipping process.

A measure of the effectiveness of those to be used according to the invention anionic polysiloxane is increasing the surface tension of the rubber latex. Optimal effectiveness is achieved in Test series determined. For this purpose, 0.25 g 0.5 g, 1.0 g and 2.0 g of the emulsions are mixed with 167 g of high-quality rubber latex (60 #ig) mixed and the mixes compared to measured pure latex.

The measurements were made with a registered tensiometer after the ring detachment of Lecomte de Nouy at 20 ⁰ C and 'the stall of 0.5 cm per minute "

The values obtained are summarized in the following table:

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Additive Additional amount (g) per I67 g natural latex

0 0.25 0.5 1.0; 2.0 surface tension (dyn / cm)

Polyaddition- 55.2 47.0 x 49.7 48.2 46.2 product A as
35 # emulsion

The latex with variously large additions of polysiloxane emulsions has a higher surface tension than the ™ pure latex *

In addition to natural latex, latices and dispersions of synthetic rubber-like polymers, polycondensates, can also be used and polyaddition compounds are used which contain relatively large amounts of soap-like emulsifiers and in their Surface tension are lower than natural latex like them z. B. by polymerization of conjugated diolefins such. B. butadiene, dimethyl butadiene, isoprene and copolymerization of such = conjugated diolefins with polymerizable vinyl

W ' compounds such as B. styrene * ot-methylstyrene, acrylonitrile, methacrylonitrile or by polymerization or copolymerization of isoolefins such as isobutylene, optionally with conjugated diolefins. Latices of polymers obtained from chlorobutadiene or its copolymers with mono- and / or diolefins or polymerizable vinyl compounds are also suitable. Furthermore, latices of polyurethanes can also be used, which are known in the known manner from high molecular weight compounds with reactive

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-BATH

capable hydrogen atoms such as polyesters or polyethers, Polyisocyanates and optionally chain extenders are built up.

Example 1; -

One dips a glove shape in the following vulcanizable Latex mixture:

100.0 weight point natural rubber (solid)

(= 167.0 parts by weight natural latex 60 JiIg) 0.25 part by weight zinc oxide 0.80 part by weight sulfur 1.00 part by weight zinc dimethyldithiocarbaminate

(dispersed in 3.95 parts by volume of a 5 # aqueous solution of a condensation product naphthalenesulfonic acids! Sodium with formaldehyde),

this is how the aforementioned webbing occurs between the fingers, and the rubber glove dried and vulcanized on the mold shows a strong reduction in wall thickness between the fingers, which leads to faulty products. .

If you add 2 parts by weight of a water to this mixture aqueous emulsion of the polyaddition product A is not added the formation of webs, which means that the liquid latex film runs evenly between the fingers takes place and thus a uniform wall thickness is achieved.

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Example 2s

In the vulcanizable latex mixture from example 1 2.5 parts by weight of a 35 # strength emulsion of the polyaddition product B stirred in. When dipping a glove shape, the modified latex runs evenly and without streaks and provides a rubber glove of uniform wall thickness between the fingers.

Example 3;

When using 1.5 parts by weight of the polyaddition product C in the form of a 40 # emulsifier-free emulsion are the same good results obtained as in the previous examples.

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Claims (2)

Patent claims: 1. Use of organosilicon compounds as Swim prevention means in the production of dipping articles by the latex dipping process from natural or synthetic latex, characterized in that the organosilicon compound a higher molecular weight, salt group-bearing anionic polysiloxane is used, which is based on the isocyanate polyaddition process made of polysiloxanes with reactive hydrogen atoms with a molecular weight of 600-4000, polyisocyanates and a compound having at least one amino group with at least a hydrogen atom reacting with isocyanate groups and at least one carboxylate and / or sulfonate group and optionally low molecular weight chain extenders with reactive hydrogen atoms has been obtained. 2. The method according to claim 1, characterized in that the higher molecular weight, salt group-bearing anionic polysiloxane is used in the form of an aqueous emulsifier-free emulsion. Le A 10 188 - 15 109824/1898