AT513212B1 - Process for treating a surface of an elastomeric product - Google Patents

Abstract

The invention relates to a method for producing a dipped article with reduced stickiness of an inner surface of at least one latex, wherein a dip mold (8) is immersed in a dip bath in which at least one latex is contained, further for treating at least one surface of at least partially crosslinked dive article is immersed with a halogen of the dipping articles in another dipping bath, in which the halogen is generated in situ during the treatment, wherein the further dipping bath is arranged in the production line for producing the dipping article, and wherein the further dipping bath is formed as an electrolytic cell and the halogen is generated electrochemically in the further immersion bath or the further immersion bath is connected to an electrolysis cell via a line, wherein in the electrolysis cell, the halogen is generated, collected and withdrawn and is introduced via the conduit into the further immersion bath. Furthermore, the invention relates to a system for carrying out the method.

Description

Austrian Patent Office AT513 212B1 2014-05-15

Description: The invention relates to a method for producing a dipped article having reduced tackiness of an inner surface of at least one latex, wherein a dipping mold is dipped into a dipping bath in which at least one latex is contained, wherein at least one surface of the at least one is further treated partially crosslinked dipping article is immersed with a halogen of the dipping articles in another dipping bath in which the halogen is generated in situ during the treatment, wherein the further dipping bath is arranged in the production line for the production of the dipping article. Furthermore, the invention relates to a system for producing a dipping article made of a latex, comprising at least one dip tank in which the latex is contained, and at least one further dip tank, in which a surface halogenation of the dipping article is performed, and a plant for producing an elastomer profile comprising a Shaping unit for shaping the profile and a post-treatment unit for treating at least one surface of the elastomer profile.

Made of natural latex products adheres to the material disadvantage of the disadvantage that they untreated a relatively high tack, so have a high coefficient of friction. This is particularly disturbing, e.g. in rubber gloves, such as surgical or examination gloves, but also in other natural latex products which, in use, are relatively moved against another surface. However, this problem can also occur with rubber products made of synthetic latices.

To reduce the stickiness of elastomer surfaces, a wide variety of methods are known from the prior art. A widely used process is the so-called halogenation. The rubber surface is treated with chlorine, more rarely bromine, whereby the surface is artificially aged and thus harder. For this purpose, the rubber product can be immersed, for example, in a dipping bath, in which the halogen is introduced from a gas cylinder. Associated with this are correspondingly elaborate provisions for the manipulation of these gas cylinders.

In the prior art, however, a method has been proposed in which the halogen required for halogenation is generated in the plant for the production of rubber gloves itself. Thus, DE 38 53 948 T2 describes a process for the surface treatment of powder-free surgical gloves made of natural rubber by halogenation. The method comprises the steps of: - putting the glove on a handshaped mold, - immersing the glove for 1 to 60 seconds in a sodium hypochlorite solution, the concentration of effective chlorine in the solution being in the range of 0.1 immersion of the glove in a hydrochloric acid solution for 1 to 60 seconds with the concentration of effective chlorine in the solution in the range of 0.1 to 1.5%, [0008] Washing the glove with water until all chlorine residues have been removed, removing the glove from the mold and turning the glove inside out and putting the glove over the hand shaped mold, immersing the glove for 1-60 Seconds in a sodium hypochlorite solution, wherein the concentration of effective chlorine in the solution is in the range of 1 to 1.5%, - immersing the glove in a hydrochloric acid solution for 1 to 60 seconds wherein the concentration of effective [0012] at least three times repeating the latter two steps to obtain a different degree of halogenation at the inner surface in the solution To obtain comparison to the outer surface; and - washing the glove with water until all chlorine residues have been removed.

The immersion of the glove in the hydrochloric acid solution causes a degradation reaction by adhering to the surface of the glove sodium hypochlorite, wherein chlorine gas is generated. Compared to processes in which chlorine gas is introduced into water in gaseous form, this method achieves the advantage that the location at which the chlorine gas is generated is narrowly defined and thus less chlorine gas is released into the environment.

Although this method already has significant advantages in comparison of the direct supply of chlorine gas in the water mixture of the immersion bath, and although it is also noted in this document that can be better regulated by this method, the halogenation, this halogenation method but still adheres to the detriment of controllability, especially with regard to product quality, since the amount of chlorine gas produced depends strongly on the amount of sodium hypochlorite on the glove and on the sodium hypochlorite concentration in the first bath. Both factors are not or can not be controlled to the required extent in large-scale production, as used for the bulk glove. Thus, the adhered amount of the sodium hypochlorite on the glove varies greatly, producing gloves with a wide range of halogenation degree of tolerance. On the other hand, the concentration of sodium hypochlorite in the first immersion bath by the immersion of the gloves constantly decreases, so that a desired concentration can be maintained in this immersion bath only with a higher effort.

DE 23 58 427 A describes a process for the surface treatment of soles of synthetic elastomers for improving the coatability and the adhesiveness of these surfaces Ver adhesible by exposure to halogen, wherein exposing the surfaces of the action of the electrolysis products of an electrolyte. The device for carrying out this method essentially provides an anode and a cathode for immersion in the electrolyte, a voltage source for generating the required potential difference between the anode and the cathode, and a holder which supports the shoe sole to be machined with its surface to be processed holds on to the anode so that the electrolysis products can act on the surface to be processed.

From DE 11 02 111 A a frame for diaphragm electrolysis cells with bipolar graphite electrodes is known, in which at the lower end of the frame an inlet channel and at the upper end of the frame collecting channels for the electrolysis products, the anolyte and the catholyte are provided wherein in the frame preferably two in-line bipolar electrode body are arranged, each having on its cathode side a diaphragm.

US 2,209,333 A describes inter alia. the treatment of rubber-like substances in an electrolytic medium of oxidizing acids and chlorinating agents.

It is the object of the present invention to provide a method of treating at least one surface of an at least partially crosslinked elastomeric product with a halogen having a higher degree of reproducibility.

This object is achieved with the aforementioned method, according to which the further dip is formed as an electrolytic cell and the halogen is generated electrochemically in the further dip or that the further dip is connected to an electrolytic cell via a line, wherein in the electrolytic cell the halogen is generated, collected and withdrawn and introduced via the line into the further immersion bath. However, the object of the invention is also achieved by a system for producing a dipping article made of a latex, in which the at least one further immersion tank is formed as an electrolytic cell with at least one anode and at least one cathode or in which the dipping 2/5 Austrian Patent Office AT513 The first part is designed as an electrolysis cell and a second part is designed for surface halogenation, wherein the two parts are flow-connected to one another, or by a system for producing an elastomer profile, in which the aftertreatment unit is formed as an electrolytic cell with at least one anode and at least one cathode or in which the aftertreatment unit is at least two parts, wherein a first part is formed as an electrolytic cell and a second part for the treatment of the surface of the elastomer profile is formed, wherein the two parts with each other are fluidly connected.

The advantage here is that the electrochemical process for the production of the halogen, in particular of the chlorine gas, is easily controlled and regulated by the electrical parameters, so that the required chlorine gas can be generated as needed in the required amount. The process is thus independent of pretreatment steps, such as the appearance of a certain amount of sodium hypochlorite. It can thus be carried out subsequently with only one halogenation halogenation. In other words, at least two different immersion baths as described in the prior art are not required. In addition, by simply adjusting the electrical parameters, the degree of halogenation can be varied, so that, if desired, a glove can be halogenated on both sides with just one dip, the treatment being able to be carried out to different intensities. It can thus be easily adapted to the roughness of the individual surfaces or partial areas of the different application areas of the elastomer product. The entire system can thus be simplified, in particular the process time can be shortened. In addition, with this method, the known advantages are achieved, such as the elimination of handling chlorine gas cylinders, etc. A further advantage is that e.g. Chlorine gas from a relatively unproblematic raw material, namely a brine, can be produced so that can be dispensed to large amounts of problematic chemicals such as hydrochloric acid or sodium hypochlorite. The process and the system can thus be made more environmentally friendly.

Preferably, the halogen is in an electrolysis cell hegestellt, in which the cathode compartment is separated from the anode compartment by a separator. On the one hand, it makes it possible to prevent the risk of chlorine gas formation, on the other hand can thus reduce the energy consumption and thus improve the efficiency. In addition, the environmental impact can be further reduced. In particular, when using a membrane as a separator, highly pure chlorine can be produced in which only small traces of oxygen are contained, whereby the quality of the elastomer product can be further improved.

It is also advantageous if the treatment of the surface of the elastomer product at a pH between 1.5 and 3, preferably at a pH of 2, is performed. In this area, the control of the degree of halogenation of the surface at high process speed is particularly easy to regulate. The process of halogenation is thus easier embedding in a large-scale glove manufacturing process, in particular so that the clock speed of the glove production is not limited by the process step of halogenation.

High cycle speeds are also achieved when the treatment of the surface of the elastomer product is carried out at a temperature between 23 ° C and 30 Ό.

According to the method, a dipping article, in particular a glove, produced, wherein a mold is immersed in a dip in which at least one latex is contained. In this application, the method offers the advantage that a changeover between different products with different levels of halogenation of the surface is easy to carry out, without the need for elaborate volumetric flow regulation, as is the case with the use of gaseous chlorine from gas cylinders.

According to a variant of the system it is provided that the at least one 3/16 Austrian Patent Office AT513 212B1 2014-05-15

Cathode is designed as a gas diffusion cathode (oxygen-consuming cathode). On the one hand, a further reduction of the energy consumption can be achieved, on the other hand, the formation of hydrogen can be avoided, whereby the danger of the chlorine gas reaction can be virtually completely eliminated. In particular, the use of radiation-induced crosslinking of the elastomers in a system with the above-described in-line generation of halogens for halogenation of the elastomer surfaces can thus also be used.

For a better understanding of the invention, this will be explained in more detail with reference to the following figures.

In a schematic simplified representation: [0029] FIG. 1 shows a variant of a dive article in a sectional view; Fig. 2 shows a variant of a method for producing a dive article in the manner of a flow chart.

By way of introduction, it should be noted that the positional information chosen in the description, such as. top, bottom, side, etc. related to the immediately described and illustrated figure and are to be transferred to the new situation mutatis mutandis when a change in position.

It should be noted in advance that the term halogenation in the context of the invention, the treatment of a surface of an elastomer is understood with an elemental halogen. This does not necessarily or not necessarily mean that halogen atoms are chemically bound to this surface.

Chlorine is preferably used as the halogen, but in the following, bromine, fluorine and iodine are not excluded.

In a first embodiment of the invention, the elastomer product is a so-called dipping article. These are, in particular, gloves, for example medical surgical and examination gloves. The elastomer products may also be catheters, condoms, finger cots, bathing caps, swim fins or protective gloves for working in clean room areas, etc.

Fig. 1 shows a variant of an immersion article in the form of a glove 1 in cross-section with a carrier layer 2 and a layer 3, which is arranged on an inner surface 4 of the carrier layer 2. In addition, on the inner surface 4 opposite outer surface 5 of the support layer 2 is also a layer 6, which, however, in the submersible article according to the invention as well as the layer 3 does not necessarily have to be present.

This layer 6 is e.g. intended to reduce the possibly existing lubricity of the outer surface 5 of the carrier layer 2, in order to form with the glove 1, for example, tools, such as e.g. Surgical instruments to be able to better grip and work better. Of course, this layer 6 can also be given other functions by having this layer 6, e.g. is equipped with an antibacterial agent, if this is not already present in the carrier layer.

Of course, it is also possible that further layers are attached to both the inner surface 4 and the outer surface 5. So it is e.g. it is conceivable to provide a layer 6 on the inner surface 4 which contains a lotion, e.g. with aloe vera or the like., In order to avoid the drying of the skin of the wearer, or to provide an appropriate antibacterial equipment in the interior of the glove 1.

It should be expressly understood, however, that the glove 1 or generally the submersible article or the elastomer product can be formed in one layer from the carrier layer 2 consisting.

To explain, it should be noted that the inner surface 4 is that surface in the embodiment of the invention as glove 1 pointing towards the skin of the wearer of the glove 1, FIG. and accordingly, the outer surface 5 is formed opposite thereto.

The carrier layer 2 consists of or comprises a crosslinked elastomer, i. a polymer with soft elastic properties at service temperature. The crosslinking can be carried out by known measures, for example with sulfur or sulfur-containing compounds, peroxidically, by means of UV light or generally actinic radiation, as known from the prior art.

The carrier layer 2 is preferably selected from a group comprising natural rubber, enzymatically deproteinized natural rubber in order to further reduce the allergy potential, isoprene rubber, polychloroprene rubber, polyurethane, nitrile rubber, isobutene-isoprene rubber, styrene-butadiene rubber, Copolymers of ethyl acrylate or other acrylates with a proportion of a monomer that facilitates vulcanization, such as Chloromethyl acrylate, further terpolymers of ethylene, propylene and an unsaturated diene, e.g. 5-ethylidene-2-norbornene, cyclopentadiene, ethylene / propylene copolymers, further polyester urethanes, thermoplastic elastomers, e.g. vinyl-based thermoplastic elastomers, thermoplastic polyurethane elastomers, olefin-based thermoplastic elastomers, polystyrene-based thermoplastic elastomers, thermoplastic polyester elastomers, thermoplastic polyamide elastomers, and mixtures thereof. The latices can therefore be of both natural and synthetic origin.

The layers 3, 6 may be prepared by spraying onto the carrier layer 2, by dipping, by brushing a corresponding polymer solution, e.g. in the form of a lacquer, or be applied by other coating methods.

The preparation of the dive article according to the invention in the embodiment of glove 1 essentially follows those process steps for glove-dipping processes which are known from the prior art.

In Fig. 2, a possible process flow is shown for this purpose.

It should already be mentioned at this point that the preparation of the dipped elastomeric articles in a discontinuous, working by a batch process dip system or preferably continuously, for example in a so-called chain dipping plant takes place.

Such thin-walled, elastic rubber and / or plastic articles, such as. As a glove, are obtained by immersing a mold at least once, the shape of which at least substantially similar to the shape of the product to be produced in a dip containing a latex.

For the production of preferably powder-free gloves 1 made of an elastomer or of a latex, a plurality of immersion molds 8, e.g. made of porcelain, plastic, metal, aluminum or the like., In the form of a glove 1 are arranged. The dipping forms 5 can be provided with a smooth surface or with a surface structuring, wherein the surface structuring improves the attractability of the gloves 1 by reducing the surface area of the gloves 1 coming into contact with the hand. However, it is also possible in this way to provide the outer surface of the gloves with a surface structuring. Conventionally, the dipping forms 8 are cleaned prior to use in the production process of possibly remaining residues from previous productions, e.g. to ensure powder-free.

Powder freedom means that no separate slip powder to improve the attractability of the glove 1, are applied. However, powdery substances which are used in the dipping process, e.g. Coagulants, be present in small quantities on the glove 1.

However, within the scope of the invention it is also possible to manufacture powdered gloves so that such sliding powders can be applied to the inner surface 4 of the glove, although this is not the preferred one Embodiment of the dive article in the embodiment glove 1 is. For gloves 1 different diving products, where the powder problem does not exist, but the application of lubricants is nothing in the way.

The purified dipping forms 8 can subsequently be dipped optionally into a first dip tank 10, in which an aqueous coagulation solution 9 is located. This may contain, for example, calcium nitrate, polyethylene glycol and a water-soluble silicone type or chalk. However, any other compositions known in the art for this purpose, e.g. Alcohol solutions of potassium or calcium salts, which may also contain release agents, e.g. Talc or calcium carbonate which, if acid soluble, can be dissolved out of the surface layers of the glove 1 in subsequent acid treatment steps.

As indicated by the arrow 11, arranged on the mold carrier 7 Tauchformen 8 are immersed in the dip tank 9, then taken out of this according to arrow 12 and optionally after an intermediate drying with a drying device - as symbolically by a hot air blower 13 and the heated air for drying schematically representing arrows 14 indicated - spent according to the dotted lines 15 to a second dip tank 16.

Of course, it is within the scope of this inventive method to those skilled in the decision whether the immersion of the dipping molds 8 always takes place in the same dip tank 9 and this via an inlet 17 and a drain 18, e.g. via a schematically illustrated conveyor 19, for example, a pump, alternately with the coagulation solution 10 or any other liquids or media that are needed for the manufacturing process, is filled or whether several consecutively arranged basin are provided for diving. It is also possible that the immersion of the dipping forms 8 by a relative movement of any kind between the mold carrier 7 and the dip tank 9, 16 takes place. Of course, it is also possible that especially those treatment or process steps in which the diving articles or gloves 1 are already removed from the dipping forms 8, in rotating containers, such as drums or the like., As in conventional washing and drying machines be used to move them during the treatment by continuous rotation of the drum, for example, to prevent sticking of the diving products or gloves 1 during production.

Since all these different possibilities for carrying out the method are known to the person skilled in the art, the description of the different apparatuses for carrying out the individual method steps is omitted and this is explained only with reference to the purely schematic representations in FIG ,

After this optionally completed intermediate drying of the coagulant or the coagulation solution 10, the immersion molds 8 are immersed in the dip tank 16, so that the immersion molds 8 immerse completely under a liquid level 20. In this dip tank 16 there is a dispersion of at least one above-mentioned elastomer for the carrier layer 2. This dispersion may contain further auxiliaries or compounding substances, such as e.g. Zinc oxide, accelerators, stabilizers, waxes, anti-aging agents, antioxidants, viscosity regulators, plasticizers, e.g. Dioctyl phthalate or diisononyl phthalate, fillers, dyes, etc., as known to those skilled in the art, e.g. from "Röthemeyer / Summer - Rubber Technology, 2001, Hanser-Verlag (ISBN 3-446-16169-4) " are known contain. With regard to the concentrations of the individual ingredients of the compounding of the latex, reference is also made to the relevant prior art.

The immersion molds 6 remain in the dip tank 16 until a desired layer thickness of the liquid elastomer or latex has formed on the surface of the immersion molds 8 or the layer of the coagulation solution 10. For this purpose, it is also possible for the immersion forms 8 to be pulled out of the immersion basin 16 several times in accordance with the arrows 12, 11 and to be submerged again.

Thereafter, according to the dotted line 15, a brief intermediate drying of the elastomeric film on the dipping molds 8, for example with hot air from a further drying device 13, e.g. a hot air blower, made, for which the air can have a temperature of 70 ° C to 140 ^, preferably 90 Ό to 110 ° C, and the dipping forms 8 of this hot air 15 sec. To 60 sec. Can be exposed. The duration of the Heißluftbeaufschlagung and the temperature of the hot air may be controlled so that the layer of the liquid elastomer on the surface passes from the liquid to the gel or solid state. However, the intermediate drying can be omitted if the elastomeric film already has sufficient strength.

Then, the mold carrier 7 with the immersion molds 8 as shown in arrow 11 can optionally be immersed in the dip tank 21 for the production of the layer 3.

At this point, it should be mentioned for the sake of order that the elastomer or the coagulation solution 10 or generally the Tauchcompoundierungen one or more known to those skilled in the art in different embodiments viscosity regulator may be added to the dipping baths to the desired Adapt flow properties. This makes it possible to adjust the viscosity of the usual manner as dispersions present products or materials to the particular desired applications to achieve appropriate thicknesses during dipping or uniform deposition of the various materials on a surface of the dipping molds 8.

For the sake of order, it should also be mentioned at this point that in the present description the term "elastomer " or "latex" regardless of whether it is a dispersion or the cured, dry, crosslinked layer or solid phase of this material, even though such as e.g. in natural latex is commonly referred to as rubber. It would therefore also be possible to designate the layers formed from the individual aforementioned materials as rubber layers.

After lifting out of the mold carrier 7 with the immersion molds 8 from the dispersion of the polymeric raw material 22 for producing the layer 3, the latter can, as indicated schematically, if necessary, also with hot air, for example at a temperature between 70 ° C and 140 ° C, preferably 90 ° C to 110 ° C, over a period of 15 sec. To 60 sec. Dried. Preferably, the temperature and the duration of the hot air treatment are adjusted so that at least the surface of the layer 3, but preferably the entire layer 3 solidifies.

Instead of or in addition to this, the dipping forms 8 with the semifinished products of the dipping articles or gloves 1 located thereon can be dipped into a further dipping basin 23 in which they are sprayed or rinsed with hot water 24. For this purpose, this by means of a pump 25 by a boiler or a heat exchanger 26, by which it is maintained at a desired temperature between 40 ° C and 95 ° C, preferably 70 ^ to 90 ° C, are circulated through the dip tank 23 ,

After this optional hot water treatment, which can last between 15 sec. And 8 min., Preferably 30 sec. And 4 min., The gloves 1 are removed from the dip tank 23 in their position mounted on the dipping molds 8, so that the remaining water 24 can drain.

The gloves 1 removed from the water 24 are left outdoors or exposed to predrying by means of hot air over a period of 10 seconds to 180 seconds, preferably 20 seconds to 50 seconds, serving as dewatering time, before being exposed to hot air the "dip tank 27", in this case a heating cabinet or a heating oven, by means of heat and / or infrared radiation are applied to start the crosslinking reaction.

Instead of or in addition to this heat treatment, the crosslinking may also be effected by means of radiation, e.g. Electron beams, ultraviolet rays, gamma rays, microwaves. The radiating surfaces 28 for the infrared radiation, which are preferably designed as tile surfaces, can have a temperature such that the crosslinking takes place in a temperature range with a lower limit of at least 85 ° C., in particular at least 90 ° C, preferably at least 150 ° C and an upper limit of 180 ° C, in particular 190 ° C, preferably 195 ° C, takes place. The dipping articles or gloves 1 can be exposed over a period of time between 1 min and 5 min to this infrared radiation schematically indicated by arrows 29. In this case, ambient air can be blown through the heat chamber or the dryer or the dip tank 27 through the plunge pool 27 or a corresponding drying device by means of a fan 30 according to the schematically indicated arrows 31.

It is also possible that the crosslinking of the elastomer of the carrier layer 2 takes place only via a hot air blower.

After drying the dipping articles or gloves 1, as shown in Fig. 2, the immersion molds 8 are immersed in a dip tank 32 in which a release agent 33, such as a powder such as talc, chalk or corn starch powder or a silicone emulsion located, which is to prevent the subsequent stripping of the gloves 1 of the diving molds 8 and simultaneous turning a sticking together now turned outward surfaces of the gloves 1. However, this process step is not absolutely necessary.

After stripping the gloves 1, for example, in a transport basket 34, which may also be provided with lattice-shaped or perforations filled, and this transport basket 34 is introduced into a dip tank 35 for halogenation, in which a raw material 36 for generating the halogen located, as will be explained in more detail below.

However, there is also the preferred possibility that the gloves 1 on the dipping forms 8 are located through the dip tank 35 or generally by several or all plunge pools of the dipping system are performed, as is the case with chain dipping. In this case, the turn of the gloves 1 takes place only at a later removal of the diving forms. 8

Following this treatment, the gloves 1 are washed at least once, but preferably several times, in water or liquids known from the prior art in order to remove the residues of halogenating agents or acids, etc., or to generally leachable substances.

When this washing operation is completed, the gloves 1 are transported to the transport basket 34 in a dip tank 37 or in a drying chamber, in which either by in the drying chamber or in a Ansaugluftweg the air for air drying heater 38 may be arranged so that the drying takes place by means of the air indicated schematically by arrows 39, which can be passed through a fan 40 or a blower through the interior of the drying chamber.

Of course, any other form of drying is possible. Thus, for example, using drums or the like .. It is preferably possible when using such a drying chamber, via an additional line 41 to inject a silicone emulsion in the air stream at the end of the drying process or at the end of the drying process, for example, the outside and optionally To coat the inner sides of the glove 1 forming surfaces with silicone and thus to improve the Anziehbar-speed of the gloves 1. Of course, it is also possible to carry out this silicone coating in just as known manner by immersion in emulsions or by spray application in certain areas of the gloves 1.

After the drying process carried out in the dip tank 37, the gloves 1 are paired together and the other processing operations, such as sterilization and packaging supplied.

For the production of a dive article according to the invention, it is not absolutely necessary that all individual steps of the illustrated process sequence are carried out. Thus, e.g. to dispense with individual water treatments. According to the invention, however, the method necessarily comprises the steps of applying a carrier layer 2 and the halogenation of at least one surface of the gloves 1.

The carrier layer 2 may have a thickness between 100 gm and 300 gm.

In order to improve the lubricity of the gloves 1 on the one hand and the attractability of the gloves 1 on the other hand, its inner surface can be halogenated, which is known to reduce the stickiness of the elastomer product.

In principle, the outer surface can be halogenated if necessary, to which the gloves 1 must be turned before.

It is also possible that the gloves 1 or the elastomer products are halogenated only in partial areas of at least one of the surfaces or it is possible that the halogenation of different partial areas or the inner and the outer surface to a different degree of halogenation takes place, for which the duration of the halogenation may be different.

The halogenation of rubber products is known in principle from the prior art.

According to the present method it is provided that the halogen is generated electrochemically in situ during the treatment. For this purpose, the dip tank 35 is preferably designed as an electrolytic cell. In this dip tank, at least two electrodes, i. arranged at least one anode 42 and at least one cathode 43 and electrically conductively connected to a power supply, not shown. These two electrodes can be arranged so that the gloves 1 are passed between these two electrodes. For example, they can each be arranged in an edge region of the dip tank 35. But it is also possible that the two electrodes are arranged adjacent to each other and the gloves 1 and the diving products are guided laterally past the electrodes.

In this dip tank 35 is the raw material 36, from which the halogen is generated. The raw material 36 is preferably a brine solution, ie a NaCl solution in the event that chlorination takes place as halogenation.

However, instead of a brine solution, an alkali halide solution, e.g. a KCI solution can be used or all chemical substances from which electrolysis chlorine can be produced, provided that these substances have no negative effects on the latex or the elastomer.

If bromination takes place instead of chlorination, the raw material 36 may comprise, for example, NaBr and / or KBr, in the case of iodination NaJ and / or KJ and in the case of fluorination NaF and / or KF.

The dip bath may consist of or comprise this brine solution.

It is advantageous if, for halogenation of the glove 1 or of the dipping article, the dipping bath has a concentration of NaCl which is selected from a range with a lower limit of 1% by weight and an upper limit of 5% by weight. -%.

But it is also possible to submit the NaCl in a concentration selected from a range of 2 wt .-% to 4 wt .-% or in a concentration of 2 wt .-% to 3 wt%.

These concentrations are also applicable with respect to NaBr and / or KBr in the case of bromination, to NaJ and / or KJ in the case of iodination and to NaF and / or KF in the case of fluorination.

The electrochemical decomposition of the NaCl are formed in the immersion tank 35 of a chlorine gas on the one hand and on the other hand NaOH. The sodium hydroxide solution is withdrawn discontinuously or continuously from the dip tank 35 in order to avoid an excessive shift in the pH of the dip bath.

In all the methods according to the invention, it is further possible that the raw material 36, so for example, the NaCl brine, is replenished discontinuously or continuously into the dip tank 35, depending on the consumption of the halogenation.

In the preferred embodiment of the method, the halogen in an electrolysis cell, ie in particular the dip tank 35, prepared in which the cathode compartment is separated from the anode compartment by a separator 44 from each other.

This separator 44 may be formed by a flow and cation permeable, porous partition. It is thus avoided that the halogen, in particular the chlorine gas, comes into contact with the hydroxide ions formed at the cathode and disproportionates. The partition can be constructed, for example, based on polytetrafluoroethylene.

However, a cation exchanger membrane may also be used as separator 44, again based on PTFE, for example, which is impermeable to the anions of the dip bath. Such a material is available, for example, under the name Nation®. It is a polytetrafluoroethylene with negatively charged SO3 residues. After both the OH-ions and the Cl2 remain in the cathode compartment, in this process variant, a hypochlorite solution is generated from which in turn chlorine gas can be generated by reaction with hydrochloric acid. It is therefore advantageous if the pH of the immersion bath in the dip tank 35 has a value between 1.5 and 3, in particular 2. The pH is adjusted and / or regulated in particular by continuous or discontinuous addition of hydrochloric acid, preferably with a concentration of from 10% by weight to 30% by weight.

In general, in all processes, it is advantageous if the treatment of the surface of the elastomer product, that is, for example, of the glove 1, at a pH between 1.5 and 3, in particular at a pH of 2, is carried out.

It is also advantageous if the production of the halogen is carried out at a potential difference between at least one cathode 43 and at least one anode 42 of at least 4 V.

In principle, the halogenation can be carried out at room temperature. However, since the dip tank 35 is preferably integrated into the production line for producing the dipping articles, it is preferable to work at a temperature which is elevated in comparison to the room temperature. The treatment of the surface of the elastomer product can be carried out in particular at a temperature between 15 ° C and 30 ° C, preferably between 20 ° C and 25 ° C.

The residence time of the elastomer products in the dip tank 35 may be between 30 seconds and 240 seconds, in particular between 40 seconds and 60 seconds.

There is also the possibility that the elastomer products are moved during the halogenation, for example rotated.

For the sake of completeness it should be mentioned that in all methods it is possible to work with more than one anode 42 and / or more than one cathode 43, for example with two, three, four, etc.

In the event that the halogenation takes place in a dip tank 35 with the separator 44, the immersion articles are preferably in the anode compartment, ie the area in which the at least one anode is arranged, at which the halogen, in particular the chlorine gas, forms, performed. It is advantageous if the anode space is larger than the cathode space.

It is also possible that in the dip tank, in which the halogenation of the elastomer article is performed, ie in particular the dip tank 35, a Mischein- direction, so for example a stirrer, is arranged in order to achieve a better homogenization, especially when the halogenation in a halogenated water, so for example a chlorine water, is performed. By halogen water is meant a water enriched with the halogen. In the latter case, the halogenation at elevated temperature proves to be advantageous, as described above, since the solubility of the halogen in a warm water is greater. Thus, indirectly, by adjusting and / or regulating the temperature of the immersion bath for halogenation, it is also possible to set the degree of halogenation, ie, for example, the degree of chlorination, of the surface of the dipping article.

In general, however, the degree of halogenation can also be adjusted and / or regulated via the control of the electrolysis cell and / or the pH of the immersion bath. For this purpose, the applied current intensity in the electrolytic cell between 140 A and 200 A, in particular between 150 A and 160 A, amount. The current density can be between 3 kA / m2 and 6 kA / m2, in particular between 4 kA / m2 and 5 kA / m2. The pH can be adjusted and / or varied and / or regulated in the above-mentioned range.

In the preferred embodiment, the dip tank 35 is located in the production line for the production of the dipping articles, that is arranged in-line. But there is also the possibility that the dip tank 35 is placed separately from the remaining parts of the production line. In this case, the generated chlorine gas or the halogen is collected in the electrolytic cell and withdrawn and fed via a corresponding line to a dip tank, which is arranged in the production line and in which the halogenation is carried out. In this case, of course, the dip tank 35 need not be designed as a dip tank, but may be formed as a conventional electrolytic cell, as is generally known. However, there is also the possibility that the elastomer products are halogenated in a separate plant which comprises the dip tank 35, which is therefore not part of the production line of the elastomer products or of the dipping articles. In this case, an additional manipulation step is required to transfer the elastomeric products from the plant for their manufacture to the plant for halogenation.

But it is also possible that in outside of the Halogenierungstauchbeckens arranged for the elastomeric electrolysis cell whose content is circulated in the halogenation and thus provided with HCl, the final concentration of Cl2 is between 300 ppm and 1200 ppm.

The at least one cathode 43 is preferably made of a ferrous material, in particular of steel.

The at least one anode 42 may consist of titanium or a titanium alloy, preferably with a ruthenium (IV) oxide coating.

There is also the possibility that in a preferred embodiment, the at least one cathode 43 is designed as a gas diffusion cathode (as a so-called oxygen-consuming cathode).

According to another embodiment of the invention can be prepared as an elastomeric product not a dipping article but an elastomeric profile and surface halogenated. The production of elastomer profiles themselves can follow the state of the art in many parts, so for example by extrusion or injection molding or by press vulcanization. Afterward, in a post-treatment unit, the halogenation, in particular the chlorination, of at least a portion of the surface of the elastomer profile takes place. For this purpose, this post-treatment unit is designed as an electrolytic cell, as described above. To avoid repetition, reference is therefore made to the above statements.

For the sake of order, it should finally be pointed out that in order to better understand the structure of the dipping system, these or their components have been shown partly unevenly and / or enlarged and / or reduced in size. 11/16 Austrian Patent Office AT513 212B1 2014-05-15

Reference Number 1 glove 36 raw material 2 carrier layer 37 dip tank 3 layer 38 heating element 4 inner surface 39 arrow 5 outer surface 40 fan 6 layer 41 line 7 mold carrier 42 anode 8 dip 43 cathode 9 dip tank 44 separator 10 coagulation solution 11 arrow 12 line 13 dip tank 14 inlet 15 outlet 16 Conveyor 17 Liquid level 18 Plunge pool 19 Raw material 20 Plunge pool 21 Water 22 Raw material 23 Plunge pool 24 Water 25 Pump 26 Heat exchanger 27 Plunge pool 28 Radiation surface 29 Arrow 30 Fan 31 Arrow 32 Plunge pool 33 Release agent 34 Transport basket 35 Plunge pool 12/16

Claims (7)

Austrian Patent Office AT513 212B1 2014-05-15 Claims 1. A process for producing a dipped article having reduced tackiness of an inner surface of at least one latex, wherein a dipping mold (8) is immersed in a dipping bath in which at least one latex is contained for the treatment of at least one surface of the at least partially crosslinked dipping article with a halogen of the dipping articles is immersed in a further dipping bath in which the halogen is generated in-situ during the treatment, wherein the further dipping is arranged in the production line for the production of the dipping article in that the further immersion bath is formed as an electrolysis cell and the halogen is generated electrochemically in the further immersion bath or that the further immersion bath is connected to an electrolysis cell via a line, wherein in the electrolysis cell, the halogen is generated, collected and withdrawn and via the line i n the further immersion bath is initiated. 2. The method according to claim 1, characterized in that the halogen in an electrolysis cell in which the cathode space from the anode compartment by a separating device (44) is separated from each other. 3. The method according to any one of claims 1 or 2, characterized in that the treatment of the surface of the elastomer product is carried out at a pH between 1.5 and 3. 4. The method according to any one of claims 1 to 3, characterized in that the treatment of the surface of the elastomer product is carried out at a temperature between 23 ° C and 30 ° C. 5. Plant for producing a dipping article made of a latex, comprising at least one dip tank (23) in which the latex is contained, and at least one further dip tank (35) in which a surface halogenation of the dipping article is performed, characterized in that the at least a further dip tank (35) as an electrolytic cell with at least one anode (42) and at least one cathode (43) is formed or that the dip tank is at least divided into two, wherein a first part is formed as an electrolytic cell and a second part is designed for surface halogenation, wherein the two parts are fluidly connected to each other. 6. plant for producing an elastomer profile comprising a shaping unit for shaping the profile and a post-treatment unit for treating at least one surface of the elastomer profile, characterized in that the post-treatment unit is formed as an electrolytic cell with at least one anode (42) and at least one cathode (43) or in that the aftertreatment unit is at least two-parted, wherein a first part is designed as an electrolysis cell and a second part is designed to treat the surface of the elastomeric profile, the two parts being flow-connected to one another. 7. Plant according to claim 5 or 6, characterized in that the at least one cathode (43) is designed as a gas diffusion cathode (oxygen-consuming cathode). 3 sheets of drawings 13/16