CA2841209A1

CA2841209A1 - Protective glove with a textile lining

Info

Publication number: CA2841209A1
Application number: CA2841209A
Authority: CA
Inventors: Mattias FINZELBERG
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-07-08
Filing date: 2011-12-22
Publication date: 2013-01-17
Also published as: US20150033801A1; WO2013007274A1; DE102011107443A1; EP2729288A1

Abstract

The invention relates to a protective glove, comprising a textile lining and a polymer layer that has an elastomer having isoprene units. According to the invention, the textile lining or textile layer and polymer layer are present as a layer composite. The invention further relates to a method for producing such a protective glove.

Description

REX-Gummitechniken GmbH &Co. KG 6.
Januar2014 Protective Glove with a Textile Lining Description Field of the Invention The invention relates to protective gloves, in particular elastic, polymeric protective gloves with a textile lining, as well as to a method for their manufacture.
Background of the Invention Because of the availability of a number of suitable polymers, it is possible to obtain protective gloves for a large number of chemical substance classes. It is thus possible, depending on the polymer or polymeric composite materials used, to obtain long permeation times for different substance classes. In particular, elastomers such as isoprene rubbers also feature a low gas permeability, which is desirable from a safety standpoint. Consequently, however, protective gloves composed of polymeric materials are not breathable, i.e. the moisture generated by perspiration remains inside the glove. This has a significant negative impact on the wearing comfort of such a protective glove, particularly when it is worn for long periods. To improve the wearing properties, in particular to absorb moisture, therefore, textile inner gloves are generally used. The use of a textile inner glove and a separate polymeric protective glove, however, is disadvantageous for practical reasons. On the one hand, it takes a relatively long time to put on the inner glove and the protective glove. On the other hand, the use of two REX-Gummitechniken GmbH & Co. KG 2 6.
Januar2014 gloves results in a relatively large overall thickness of the glove combination, which has a disadvantageous effect on tactile sensitivity. There is also often a lot of play, i.e. space between the textile inner glove and the polymeric glove, which likewise has a disadvantageous effect on tactile sensitivity.
There is thus an interest in polymeric protective gloves with a fixed textile lining. In this connection, there are protective gloves known from the prior art in which the textile lining is glued into the polymer protective glove, i.e. an adhesive agent is used to affix the lining in the glove. The textile lining and the polymeric material, however, do not have a common phase boundary and the adhesion is produced by means of the adhesion and cohesion forces of the adhesive agent, for example a glue. The gluing process is disadvantageously complex and the textile lining and polymer glove come unglued from each other relatively easily. The latter is particularly true when the bonding agent is washed out over the course of the wearing life or is subject to other external influences.
By contrast, a protective glove made of a composite material composed of a textile knitted fabric and a polymer layer has a more powerful adhesion between the textile knit and the polymer layer.
German patent disclosure DE 27 59 008 Al describes a protective glove composed of a textile that has been coated by means of a dip-coating process from a dispersion with polymers such as polyvinyl chloride (PVC) and also describes its manufacturing method and an apparatus REX-Gummitechniken GmbH & Co. KG 3 6.
Januar2014 conceived for this purpose. Due to the irregular layer thicknesses and the occurrence of diffusion conduits, so-called "pin holes," a protective glove of this kind has a comparatively poor protective effect. This is also disadvantageous from an economic standpoint because it results in a larger number of rejects. It also requires the use of additives such as coagulation reagents.
General Description of the Invention The object of the invention is to create a polymeric protective glove with a textile lining, which has uniform permeation times across the entire surface of the glove and thus has a reliable protective effect in relation to a variety of chemical compound classes.
Another object is to create a glove of this kind that also has a high level of wearing comfort while maintaining flexibility and tactile sensitivity. Another object is to create an efficient method for manufacturing a protective glove of this kind.
This object is attained by the subject of the independent claims. Advantageous embodiments and modifications are disclosed in the respective dependent claims.
Accordingly, the invention provides a polymeric protective glove with a textile lining in which the textile lining and at least a first polymer layer are embodied in the form of a layered laminate. The first polymer layer includes a synthetic elastomer, which is embodied in the form of a copolymer with isoprene as a monomer unit, i.e. the elastomer contains isoprene monomer units. In the context REX-Gummitechniken GmbH & Co. KG 4 6.
Januar2014 of the invention, copolymers are understood to be polymers with at least two different monomer units. An isoprene monomer unit is understood in particular to be the repeating unit I. Polymers with isoprene monomer units are understood to also include those polymers in which derivatives of isoprene monomer units are present. In particular, such polymers are understood to be polymers with isoprene monomer units in which a derivatization has taken place by means of polymer analogous reactions such as halogenation of the polymer.
-N
*
The textile layer of the layered laminate forms the inside of the glove and is understood to be the bottom (innermost) layer. Consequently, the first polymer layer, like optional, subsequent additional polymer layers situated over the said layer, i.e. relative to the glove as it is worn by the user, is situated toward the outside. The layered laminate is constructed so that the textile layer and the first polymer layer are firmly bonded to each other by means of a common boundary layer. The textile layer here can, for process-related reasons, also contain additives or residual amounts of additives such as sizing agents or film-forming substances, in particular polyvinyl alcohol (PVA) or a polysaccharide such as starch.
In a preferred embodiment of the invention, the textile layer and the first polymer layer are held together by a fiber reinforced material layer, i.e. a fiber/synthetic REX-Gummitechniken GmbH & Co KG 5 6.
Januar2014 composite. This permits a particularly good adhesion of the first polymer layer to the textile lining or textile layer.
In particular, it is thus possible to dispense with using an adhesive agent, in particular a glue. The textile properties of the textile lining are thus largely preserved.
On the common boundary layer, the lining and polymer layer form a fiber reinforced material in which the fibers of the textile layer are embedded into a matrix of the polymer of the first polymer layer. The fiber reinforced material is produced when the textile lining or textile layer is dipped into a solution of a synthetic rubber with isoprene monomer units. At the boundary layer of the two layers, the polymer solution penetrates into the textile layer and envelops the fibers. The textile layer is thus at least partially penetrated by the polymer layer. An entanglement of the textile fibers with the polymer chains occurs. This increases the contact area between the fibers and the polymer chains and thus also increases the inter- and intramolecular forces of attraction that can be due to interactions such as van-der-Waals forces or adhesion effects.
Preferably, the textile lining is composed of a knitted fabric. It is advantageous if, in addition to the first polymer layer, the textile layer or textile lining is elastic.
The knitted fabric is preferably a knitted fabric with double loops; an interlock knitted fabric is particularly preferable. This is advantageous for producing a fiber = REX-Gummitechniken GmbH
&Co. KG 6 6. Januar2014 reinforced material while preserving the textile properties of the lining since the knitted fabric has a sufficient mesh density, which has a positive effect on the degree of impregnation of the textile lining.
In an advantageous embodiment of the invention, the knitted fabric of the textile lining contains cellulose-containing fibers. It is particularly advantageous if the knitted fabric is composed of cotton or a cotton blend fabric, in particular with a cotton content of greater than 50%. This is advantageous because natural fibers, in particular cellulose-containing fibers, are particularly able to absorb moisture due to their swelling capacity.
It is advantageous if the cotton fabric has a density of greater than 150 g/m2, in particular greater than 250 g/m2.
The yarn size of the yarn used is preferably 30 : 1.
It has turned out that the penetration of the textile lining can be influenced by means of the density of the knitted fabric in combination with the yarn size.
In one embodiment of the invention, the first polymer layer contains an elastomer with butyl monomer units. It is thus possible to achieve a protective effect in relation to a multitude of compound classes. Thus, elastomers with isoprene monomer units such as cross-linked butyl rubbers (IIR), in particular elastomers with butyl monomer units, have a good protective effect in relation to polar solvents and in relation to acids and bases. Low glass temperatures Tg result in a very good flexibility, even at low temperatures. Moreover, elastomers with isoprene units have REX-Gummitechniken GmbH & Co. KG 7 6.
Januar2014 a low gas permeability, i.e. they are impermeable to a multitude of gases such as hydrogen chloride or ammonia.
In a preferred embodiment of the invention, the first polymer layer contains an elastomer with halogenated butyl monomer units, in particular an elastomer with butyl monomer units that has been halogenated in a polymer analogous reaction. It is particularly preferable for the first polymer layer to contain an elastomer with bromobutyl monomer units; in the context of the invention, bromobutyl monomer units are understood in particular to be the repeating units II, III, :r and * \
IV.
Br :r II III IV
Compared to their pure hydrocarbon derivatives, halogenated butyl rubbers are easier to cross-link because of their lower bond energies. This effect is particularly pronounced in rubbers with bromobutyl monomer units. In addition, a halogenation of the butyl rubber increases its chemical inertness and thus increases the protective effect of the glove.
According to one embodiment of the invention, the first polymer layer is applied to the textile layer by means of a dip-coating process, i.e. a dipping process, in particular a dip-coating process from a solution. This is advantageous since it makes it possible to dispense with additives such as coagulation reagents. In addition, polymer layers REX-Gummitechniken GmbH & Co. KG 8 6.
Januar2014 applied by dip-coating processes from solutions have consistent layer properties. It is thereby possible to ensure constant permeation times over the entire glove and thus a reliable protection. It is likewise possible to avoid the occurrence of so-called pin holes, i.e. diffusion conduits, in the polymer layer.
Preferably, the first polymer layer is composed of two polymer sublayers: the first polymer sublayer contains no colorant, the second polymer sublayer contains colorant, and the second polymer sublayer is disposed onto the first polymer sublayer. This embodiment of the first polymer layer is particularly advantageous since uncolored, i.e.
light-colored, textile linings are typically used for protective gloves. Because an uncolored first polymer sublayer is used, the sublayer glistens through the textile lining without influencing the color impression of the lining. On the other hand, users especially prefer protective gloves in which colorants have been added to the polymer layer; hence, the established position of such gloves in the marketplace.
In an advantageous modification of the invention, at least one second polymer layer of another, different polymer is applied over the first polymer layer. In another preferred embodiment, the second polymer layer contains a fluorinated elastomer. Repulsive, i.e. repelling, interactions sharply reduce an adsorption of molecules on the layer surface, thus increasing the resistance to a large number of chemical substance classes. Consequently, the comparatively high grease, oil, and fuel permeability of the first polymer layer's elastomer with isoprene monomer units can REX-Gummitechniken GmbH & Co. KG 9 6.
Januar2014 be compensated for through combination with the second polymer layer.
Such a protective glove made of a composite material of different polymer layers, in particular a layered laminate composed of an isoprene elastomer and a fluoroelastomer, due to synergistic effects, offers a broader range of protection, i.e. high permeation times for a large number of compound classes, than corresponding protective gloves with only one polymer layer.
In an advantageous modification of the invention, the second polymer layer contains an elastomer with 1,1-difluoroethylene monomer units. Fluoroelastomers with 1,1-difluoroethylene monomer units are inert in relation to many chemicals, oils, and fuels and are heat resistant. The high tear resistance of up to 20 MPa of fluororubbers with 1,1-difluoroethylene monomer units also results in a high mechanical resistance of the polymer composite material.
In a particularly advantageous embodiment of the invention, the second polymer layer contains a copolymer with the monomers 1,1-difluoroethylene and hexafluoropropene.
In another preferred embodiment according to the invention, the second polymer layer contains an elastomer with acrylonitrile monomer units such as a cross-linked nitrile rubber (NBR).
Preferably, the protective glove has a first polymer layer with a thickness of 0.05 mm to 0.5 mm and/or a second polymer layer with a thickness of 0.05 mm to 0.15 mm. This REX-Gummitechniken GmbH & Co. KG 10 6.
Januar2014 has a particularly advantageous effect on permeation times, flexibility, and wearing comfort.
The manufacturing method is composed of at least the following steps:
In step a), a textile lining is placed onto a glove form.
In this case, it is advantageous to use an anti-friction agent such as a silicone oil, which is applied to the glove form in advance. In the next step b), a solution of a film-forming polymer is applied to the textile lining that has been placed onto the glove form. In order to produce a first polymer layer, in step c), a glove form is dipped into a first solution of a synthetic, first rubber. In order to prevent a cross-linking of the rubber either in the solution or immediately after removal of the form, the temperature Ti during the dip-coating procedure is lower than the cross-linking temperature of the first rubber. After a predefined dipping time, i.e. immersion time, the glove form is removed from the first solution (step d)). Steps c) and d) are carried out once or several times in sequence. The dipped first polymer layer is dried (step e)). Preferably, the drying time is at least 8 hours. Then in step f), the first polymer layer is vulcanized by autoclaving the protective glove. In the next step g), the protective glove is removed from the form.
In an advantageous embodiment of the method according to the invention, in step c), the glove form is dipped into a first solution of a butyl rubber, preferably a first solution of a halogenated butyl rubber, and particularly REX-Gummitechniken GmbH & Co. KG 11 6.
Januar2014 preferably a first solution of a rubber with bromobutyl monomer units.
In a modification of the invention, after step e), the glove form is dipped into a second solution of a second, other synthetic rubber. After a predefined dipping time t2, the glove form is removed from the solution and dried. In particular, the first and second polymer layers are jointly vulcanized in step f).
It is particularly advantageous if the second solution contains a rubber with the monomers 1,1-difluoroethylene and/or hexafluoropropene. This has a positive effect on the properties of the glove, for example on the permeation times for a multitude of chemical compound classes.
Usually in the solvent dipping process, i.e. a dip-coating process from a solution, however, longer immersion times are required than in the corresponding dispersion process.
When a textile lining is dipped for a long time, this typically results in a partial or even total penetration of the textile lining and thus in a loss of the desired textile properties of the lining. Pre-treating the lining with a film-forming polymer can prevent a complete impregnation of the textile lining, even with longer dipping times. It is thus possible to dip polymer layers into solutions while still maintaining the desired textile properties of the lining.
In particular, polar polymers with hydroxyl groups are used as film-forming polymers. Preferably, these polymers are water-soluble. In particular, a PVA solution and/or a REX-Gummitechniken GmbH & Co. KG 12 6.
Januar2014 polysaccharide-containing solution such as a starch-containing solution are used as a solution of a film-forming polymer. Preferably a plasticiser, in particular glycerin, is added to the film-forming polymer solution.
Surprisingly, it occurred that according to one embodiment, a spraying or a single or multiple brushing or dabbing of the textile lining with a cloth impregnated with the solution of the film-forming polymer can prevent a complete penetration with the rubber solution. It is thus possible to prevent a complete penetration of the textile lining.
This effect is particularly pronounced with cellulose-containing textiles. Cellulose-containing fibers such as cotton fibers swell significantly in the presence of moisture and absorb the moisture. The application of the film-forming polymer thus makes it possible to optimally pre-treat these fibers for the subsequent dip-coating procedure.
In one embodiment, before being dipped into the first solution of a rubber with isoprene units, the textile lining is brushed with the PVA solution until the amount of application of PVA onto the lining totals 0.15 to 3 g, preferably 0.3 to 1.8 g, particularly preferably 0.6 to 0.9 g. It is thus possible to influence the degree to which the rubber impregnates the textile lining.
According to an alternative embodiment, the textile lining is sprayed with a solution containing a polysaccharide such as starch. This solution preferably functions as a sizing agent. The use of a polysaccharide, in particular starch, as a film-forming polymer has the advantage that the REX-Gummitechniken GmbH & Co. KG 13 6.
Januar2014 protective glove does not stick very powerfully to the glove form. As a result, after production, the glove can surprisingly be removed from the glove form even without turning it inside out, which significantly improves the production process.
In one embodiment of the method according to the invention, the viscosity of the first rubber solution is from 100 to 200 s (determined with a 6 mm Ford beaker). This is advantageous because a rubber solution with a high viscosity, due to its flow behavior, penetrates more slowly into the textile lining than corresponding solutions with lower viscosities. Consequently, the selection of the viscosity of the first rubber solution constitutes a further parameter which, in combination with the film-forming polymer, can be used to influence the degree of penetration.
In a modification of the invention, the textile lining is dipped into two different solutions of the same first synthetic rubber, which differ in terms of their viscosities. First, the textile lining is dipped according to process steps c) and d) into a solution of the first synthetic rubber with a high viscosity. This produces a first polymer sublayer, which does not completely penetrate the textile layer and seals the surface of the textile lining on the outside. In the subsequent dip-coating according to process steps c) and d), the dipping takes place in a second solution of the first synthetic rubber with a lower viscosity, thus contributing to a further build-up of the first polymer layer. This is particularly advantageous for process-related reasons since rubber REX-Gummitechniken GmbH & Co. KG 14 6.
Januar2014 solutions with comparatively low viscosities are easier to work with when dip-coating from a solution.
In at least one of the dip-coating procedures, the glove form is preferably dipped partially at least once and then is dipped all the way. This makes it possible to achieve uniform layer thicknesses also with glove forms in which this would not otherwise be possible due to their geometry, for example in glove forms with sleeves that widen out in the direction of the glove opening. The partial dipping is also advantageous in terms of the degree of penetration of the textile layer. By initially pre-dipping only the hand region, it is possible to select a reduced dipping depth.
As a result, the hydrostatic pressure is lower during the first dip-coating procedure. This effect is particularly observable at the finger tips. Each dip-coating procedure of the glove form into the same rubber solution produces another layer of the rubber, which is referred to as a dipped polymer sublayer. After a dipped polymer sublayer has been deposited in the first partial dipping procedure, which seals the textile lining up to approximately the wrist, then a full dipping can occur, i.e. with a higher hydrostatic pressure at the fingers, without this disadvantageously affecting the impregnation depth of the textile lining.
A preferred embodiment of the invention provides a method in which the polymer layers are dipped as often and for as long as necessary until the first polymer layer has reached a thickness of 0.05 to 0.5 mm and/or the second polymer layer has reached a thickness of 0.05 to 0.2 mm.

REX-Gummitechniken GmbH & Co. KG 15 6.
Januar2014 The vulcanization of the first polymer layer preferably occurs by means of autoclaving at a pressure of 3 to 5 bar and/or at a temperature of 60 to 170 C, in particular at a temperature of 90 to 150 C. A cross-linking of rubbers into elastomers increases their mechanical resistance significantly. In addition, the cross-linking reduces the permeation rates within the cross-linked polymer layers.
It is advantageous to wash the removed protective gloves with water to which tensides have preferably been added.
Residues of PVA and/or starch that are not enveloped by the first polymer layer can thus be at least partially removed from the textile lining. However, one advantage in the use of starch as a film-forming polymer lies in the fact that it is possible to dispense with the use of rinsing agents when removing the protective glove from the glove form.
Furthermore, the starch can remain in the textile lining without a significant, negative impact on the wearing comfort, so that it is possible to dispense with an additional step of washing out the finished protective glove, thus making it possible to increase productivity.
The invention will be described in greater detail below in conjunction with an exemplary embodiment and with reference to the figures; some elements that are the same or similar have been provided with the same reference numerals.
Brief Description of the Figures Fig. 1 is a schematic depiction of the manufacturing method of the first exemplary embodiment, REX-Gummitechniken GmbH & Co. KG 16 6.Januar2014 Fig. 2 is a schematic depiction of the manufacturing method of the second exemplary embodiment, Fig. 3 is a schematic depiction of the manufacturing method of the third exemplary embodiment, Fig. 4 is a schematic depiction of the protective glove according to the invention, Fig. 5 is a schematic cross-section through the composite material of a protective glove with the glued-in textile lining, Fig. 6 is a schematic cross-section through the detail A of the first exemplary embodiment, Fig. 7 is a schematic cross-section through the detail A of the second exemplary embodiment, Fig. 8 is an optical microscope image of the cross-section through the detail A of the first exemplary embodiment.
Detailed Description of an Exemplary Embodiment Fig. 1 schematically depicts the manufacturing method of a protective glove 16 in conjunction with the first exemplary embodiment. Fig. 2 shows a simplified form of the manufacturing method, which is explained in greater detail in conjunction with a second exemplary embodiment. Fig. 3 shows another embodiment of the manufacturing method. Fig.
4 is a schematic depiction of the protective glove 16 according to the invention. The upper part of the protective glove 16 is composed of the fingers 17, the REX-Gunnmitechniken GmbH & Co. KG 17 6.
Januar2014 palm, and the back of the hand and at the wrist 18, transitions into the sleeve 19 of the glove. The inside of the protective glove 16 is composed of the textile lining 2. The layer structure of the layered laminate of the two exemplary embodiments will be described in greater detail in conjunction with detail A in Figs. 5 and 7.
The method schematically depicted in Fig. 1 for manufacturing the first exemplary embodiment includes the following steps:
A glove form 1 composed of ceramic is brushed with silicone oil. Then a textile cotton lining 2 is pulled on over the glove form 1. A cloth that is impregnated with a PVA
solution is used to apply 3 to 4 coats of the aqueous PVA
solution 3 to the textile lining 2. To produce the PVA
solution 3, first 3.75 kg of PVA are dissolved in 25 liters of demineralized water at 90 C. For the ready-to-use solution 3, 1 liter of the parent solution was mixed with 500 ml glycerin and 5 liters of demineralized water. The PVA solution 3 is in particular applied from the finger tips 20 to the wrist 18 by wiping with a cloth, leaving out the sleeve of the glove 19. Then the lining is dried at room temperature. In a heated dipping case 4, the glove form 1 is dipped into a dipping reservoir 5 of a first solution of a synthetic first rubber 6. The solution temperature of the solution of the synthetic first rubber 6 is Tl = 30 C during the dipping.
The first solution of a synthetic first rubber 6 contains bromobutyl rubber and toluene as a solvent. No colorants were added to the first bromobutyl solution 6. The first REX-Gummitechniken GmbH & Co. KG 18 6.
Januar2014 bromobutyl solution 6 has a viscosity of 100 to 200 s (determined with a 6 mm Ford beaker) during the dipping. In a first dip-coating procedure, the glove form 1 is partially dipped into the first bromobutyl solution 6 from the finger tips 19 to the wrist 18 and in the subsequent dip-coating procedures, is dipped into it all the way, i.e.
including the sleeve 19. In the first dip-coating procedure, the partial dipping causes a lower hydrostatic pressure to act on the textile lining, in particular on the fingers 17 and the finger tips 20, than would occur in a complete dipping. It is thus possible to reduce the penetration of the textile lining 2 by the first bromobutyl solution 6. After the drying of the first dipped polymer sublayer thus produced, the surface of the textile lining 2 is sealed, thus permitting the dipping in subsequent dip-coating procedures to be carried out with higher hydrostatic pressure at the fingers 17 and the finger tips 20. The dipping is carried out as often and for as long as necessary until the dipped polymer sublayers produced in the individual dipping procedures combine to reach a thickness of approximately 0.1 mm and thus constitute the first polymer sublayer 26 of the first polymer layer 25.
For the dipping of the glove form 1 in the bromobutyl solution 6, the lifting device 7 raises and lowers the dipping reservoir 5. After each dip-coating procedure, the glove form 1 is dried under rotation for a period of 30 minutes at 30 C.
The polymer layer 26 deposited in the first bromobutyl solution 6 and composed of a plurality of polymer dipped sublayers (not shown in detail in Figs. 6 and 7) is white.

=
REX-Gummitechniken GmbH & Co. KG 19 6. Januar2014 The glove form 1 is dried for at least 8 hours at 25 to 30 C in order to remove the solvent.
Then, in a second heatable dipping casing 8, a dip-coating in a second solution 10 of the synthetic first rubber contained in a dipping reservoir 9 is carried out. The solution temperature of the second rubber solution 10 is 30 C. The second solution of the synthetic first rubber 10 thus likewise contains bromobutyl rubber dissolved in toluene. In addition, the second bromobutyl solution 10 contains carbon as a colorant. The viscosity of the second bromobutyl solution 10 is from 50 to 120 s (determined with a 6 mm Ford beaker). The glove form 1 is dipped into the second bromobutyl solution 10 in three full-immersion dip-coating procedures until the dipped polymer sublayers deposited in this way (not shown in detail in Figs. 6 and 7) combine to produce the second polymer sublayer 27 of the first polymer layer 25 and have a thickness of approximately 0.05 mm. After each dipping procedure, the glove form 1 is dried under rotation. After the last dip-coating procedure in the second bromobutyl solution 10, the glove form 1 is dried for 12 hours at room temperature.
Then in a heatable dipping casing 11, the glove form 1 is dipped into a dipping reservoir 12 containing a third rubber solution 13. Here, too, the glove form 1 is not moved, but instead, the lifting device 7 moves the dipping reservoir 12. The third solution of a synthetic third rubber 13 contains a rubber with the monomers 1,1-difluoroethylene, hexafluoropropene, and tetrafluoroethylene, e.g. Vitone. Methyl ethyl ketone is A
REX-Gummitechniken GmbH & Co. KG 20 6.
Januar2014 used as a solvent. The temperature T2 of the Viton solution 13 is T2 = 25 C during the dip-coating procedure.
After a predefined dipping time, the glove form 1 is removed from the dipping reservoir 12 and dried for 30 minutes at a temperature of 25 C under rotation in the dipping casing 11. The above-described process of dipping in the Viton solution 13 and the subsequent drying procedure are repeated 3 to 5 times until the layer thickness of the Viton layer serving as the second polymer layer 27 is approximately 0.1 mm. In order to remove the methyl ethyl ketone completely, the glove form 1 is dried for 12 hours at room temperature. Then, the coated glove form 1 is vulcanized in an autoclave 14 for 120 minutes at a pressure of 3 bar and a temperature of 150 C. Thus, the first polymer layer 25 and the second polymer layer 28 are jointly vulcanized as a layered laminate 29 composed of different polymers.
Fig. 2 shows the manufacturing method of a second exemplary embodiment. The second exemplary embodiment has only the first polymer layer 25 and thus constitutes a simplified form of the first exemplary embodiment described above.
Here, too, the manufacturing method includes preparing the glove form 1, pulling on the textile lining 2, and coating it with a PVA solution 3. These steps are performed in accordance with the manufacturing method of the first exemplary embodiment. By contrast with the first exemplary embodiment, however, dipping is only carried out in the bromobutyl solutions 6 and 10 according to the manufacturing method of the first exemplary embodiment.
After the last dip-coating procedure in the bromobutyl REX-Gummitechniken GmbH & Co. KG 21 6.
Januar2014 solution 10, the glove form 1 is dried at room temperature to completely remove the methyl ethyl ketone. The coated glove form 1 is then vulcanized in an autoclave 14 for 120 minutes at a pressure of 3 bar and a temperature of 150 C.
Fig. 3 shows a third exemplary embodiment of the manufacturing method. The difference from the first exemplary embodiment (Fig. 1) lies in the use of a starch-containing solution 15 in lieu of the PVA solution 3. For example, the starch-containing solution is a conventional ironing or laundry starch solution thinned 1 : 1 with water.
Consequently, it is preferable for PVA and/or starch to be used as the polar polymer with hydroxyl groups. Before the first dip-coating procedure, the textile lining 2 in this case is sprayed with the starch-containing solution and is then dried in an oven (30) until the water of the starch-containing solution has completely evaporated, for 20 minutes at 80 Celsius in the example. The subsequent process steps are performed analogously to the first exemplary embodiment.
The layer structure of the first exemplary embodiment is schematically depicted in Fig. 6; dipped polymer sublayers are not shown in detail. The protective glove 16 according to the invention and the composite material according to the invention are composed of a textile layer or the textile lining 2 and the first polymer layer 25, which partially penetrates the textile layer 2. Consequently, unlike the protective glove with the glued-in lining 2 schematically depicted by way of example in Fig. 5, the REX-Gummitechniken GmbH & Co. KG 22 6. Januar2014 =

composite material according to the invention does not have a adhesive agent layer 22. The partial penetration of the textile lining 2 by the first polymer layer 25 produces a mechanical entanglement of fibers and rubber, which is fixed in place in place by the vulcanization of the rubber.
In this case, the penetration only goes so deep, as a result of which the textile properties of the lining 2 are at least partially preserved.
The textile layer or textile lining 2 forms the inside of the glove. The arrow 23 symbolizes the chemical action on the protective glove 16 from the outside.
In the first exemplary embodiment, in addition to the textile layer 2 and the first polymer layer 25, which is composed of the two polymer sublayers 26 and 27, the layered laminate of the protective glove 16 is also composed of a second polymer layer 28, as schematically depicted in Fig. 6.
The textile lining 2 of the exemplary embodiment contains cotton fibers. The cotton content is > 50%; the lining can be a cotton blend fabric or a pure cotton knitted fabric.
The knitted fabric is embodied as an interlock knitted fabric and has a weight of 265 g/m2 with a yarn count of 30.
The first polymer layer 25 is composed of bromobutyl rubber and has a layer thickness of 0.15 mm. This bromobutyl layer 25 not only acts as a barrier to liquid media, but also has a very low gas permeability. Consequently, the bromobutyl layer 25 provides protection from gases such as ammonia or REX-Gummitechniken GmbH & Co. KG 23 6.
Januar2014 hydrogen chloride. The second polymer layer 28 contains a fluoroelastomer with the monomers 1,1-difluoroethylene and hexafluoropropene and possibly also tetrafluoroethylene, e.g. Viton0. The Viton0 layer 28 has a layer thickness of 0.1 mm. The combination of the bromobutyl layer 25 and the Vitone layer 28 in the layered laminate 29 makes it possible to achieve a protective effect that goes beyond the cumulative action of the two individual layers. The exemplary embodiment has long permeation times for a multitude of compound classes such as aliphatic hydrocarbons, acids, bases, and polar organic compounds such as amines and polar solvents. The textile lining 2 simultaneously ensures a high level of wearing comfort without having a negative impact on tactile sensitivity or flexibility of the protective glove 16.
Fig. 8 shows an optical microscope image of the cross-section A of the second exemplary embodiment described above. The textile lining 2 forms the inside of the glove.
The bromobutyl layer 25 and the textile lining 2 thus form a composite material. The white, i.e. uncolored, first bromobutyl sublayer 26 here partially penetrates the textile layer 2 and seals the textile lining 2 from the outside. The second bromobutyl sublayer 27 that is colored with carbon is visible over the first bromobutyl sublayer 26.
It is clear to the person skilled in the art that the above-described exemplary embodiment is to be understood as an example and that the invention is not limited to this, but can be varied in numerous ways without going beyond the scope of the invention. It is also clear that the features =
REX-Gummitechniken GmbH & Co. KG 24 6. Januar 2014 - regardless of whether they are disclosed in the description, the claims, the figures, or in some other way - also define individual, essential components of the invention, even if they are described together with other features.

Claims

1. A polymeric protective glove (16) with a textile lining (2), characterized in that the protective glove (16) includes a textile layer embodied in the form of a textile lining (2) and at least one first polymer layer (25) composed of a synthetic elastomer with isoprene units and in which the textile layer (2) and the first polymer layer (25) are embodied in the form of a layered laminate (29) and the inside of the protective glove (21) is formed by the textile layer (2).

2. The protective glove (16) according to the preceding claim, wherein the textile lining (2) and the first polymer layer (25) constitute a fiber reinforced material at their boundary layer.

3. The protective glove (16) according to one of the preceding claims, wherein the textile lining (2) and the first polymer layer (25) are held together without an adhesive agent.

4. The protective glove (16) according to one of the preceding claims, wherein the textile lining (2) is a knitted fabric, preferably a knitted fabric with double loops, particularly preferably an interlock knitted fabric.

5. The protective glove (16) according to one of the preceding claims, wherein the knitted fabric contains cellulose-containing fibers.

6. The protective glove (16) according to one of the preceding claims, wherein the knitted fabric forms a textile lining (2) composed of a cotton knitted fabric or a cotton blend knitted fabric, in particular a cotton blend knitted fabric with a cotton content of > 50%.

7. The protective glove (16) according to one of the preceding claims, wherein the textile layer (2) has a density of > 150 g/m2, in particular > 250 g/m2

8. The protective glove (16) according to one of the preceding claims, wherein the first polymer layer (25) contains an elastomer with butyl monomer units.

9. The protective glove (16) according to one of the preceding claims, wherein the first polymer layer (25) contains an elastomer with halogenated butyl monomer units, in particular bromobutyl monomer units.

10. The protective glove (16) according to one of the preceding claims, wherein the first polymer layer (25) is composed of a layered laminate containing at least two sublayers (26, 27) of the same polymer.

11. The protective glove (16) according to claim 10, wherein the first sublayer (26) of the first polymer layer (25) contains no colorant and the second sublayer (27) contains colorant.

12. The protective glove (16) according to one of the preceding claims, wherein the first polymer layer (25) has been applied by means of a dip-coating process, in particular by means of a dip-coating process from a solution.

13. The protective glove (16) according to one of the preceding claims, wherein at least one second polymer layer (28) of a second synthetic elastomer is disposed onto the first polymer layer (25).

14. The protective glove (16) according to one of the preceding claims, wherein the second polymer layer contains an elastomer with i) 1,1-difluoroethylene and/or hexafluoropropene monomer units or ii) acrylonitrile monomer units.

15. The protective glove (16) according to one of the preceding claims, wherein the first polymer layer (25) has a thickness of 0.05 mm to 0.5 mm and/or the second polymer layer (28) has a thickness of 0.05 mm to 0.15 mm. 20

16. The protective glove (16) according to one of the preceding claims, wherein the textile layer (2) contains at least residual amounts of a film-forming polymer, in particular polyvinyl alcohol and/or a polysaccharide, preferably starch.

17. A method for manufacturing a protective glove (16) having at least the following steps:
a) placement of a textile lining (2) onto a glove form (1), b) application of a solution (3) of a film-forming polymer onto the textile lining (2) and drying of the textile lining (2), c) dipping of the glove form (1) into a first solution (6) of a synthetic, first rubber at a temperature T1, where T1 is lower than the cross-linking temperature of the first rubber, in order to produce a first synthetic polymer layer (25), d) removal of the glove form (1) from the first rubber solution (6) after a predefined dipping time, with steps c) and d) being carried out once or several times in sequence, e) drying of the dipped first synthetic polymer layer (25) until the solvent is at least largely evaporated, f) vulcanization of the first synthetic polymer layer (25) by autoclaving the protective glove (16), g) removal of the protective glove (16) from the glove form (1).

18. The method according to the preceding claim, wherein the synthetic rubber of the first solution (6) is a butyl rubber, preferably a halogenated butyl rubber, and particularly preferably a bromobutyl rubber.

19. The method according to one of the preceding claims, wherein after step e), the glove form (1) is dipped into a second solution (13) of a second synthetic rubber and after a predefined dipping time t2, is removed from the second solution (13) and dried.

20. The method according to one of the preceding claims, wherein the second synthetic rubber of the second solution (13) is halogenated.

21. The method according to one of the preceding claims, wherein the second synthetic rubber of the second solution (13) contains the monomers 1,1-difluoroethylene and/or hexafluoropropene.

22. The method according to one of the preceding claims, wherein the film-forming polymer contained in the film-forming polymer solution (3) is a polar, preferably water-soluble polymer with hydroxyl groups.

23. The method according to one of the preceding claims, wherein the solution (3) of the film-forming polymer contains polyvinyl alcohol and/or a polysaccharide, in particular starch.

24. The method according to one of the preceding claims, wherein a plasticiser, in particular glycerin, is added to the film-forming polymer solution (3).

25. The method according to one of the preceding claims, wherein the textile lining (2) is brushed with the PVA
solution (3) until the amount of application of PVA totals 0.15 to 3 g, preferably 0.3 to 1.8 g, particularly preferably 0.6 to 0.9 g.

26. The method according to one of the preceding claims, wherein the viscosity of the first rubber solution (6) is from 100 to 200 s, determined with a 6 mm Ford beaker.

27. The method according to one of the preceding claims, wherein the glove form (1) is first dipped into the first solution (6) of the first synthetic rubber and is then dipped into a second solution (10) of the first synthetic rubber and the viscosity of the first solution (6) is greater than the viscosity of the second solution (10).

28. The method according to one of the preceding claims, wherein in at least one of the dip-coating procedures, the glove form (1) is partially pre-dipped to the wrist (18) at least once and then is dipped completely.

29. The method according to one of the preceding claims, wherein the glove form (1) is dipped for as long and as often as necessary into the corresponding rubber solutions until the first polymer layer (25) has reached a thickness of 0.05 to 0.5 mm and/or the second polymer layer (28) has reached a thickness of 0.05 to 0.2 mm.

30. The method according to one of the preceding claims, wherein the protective glove (16), after the dipping procedures in the first rubber solution (6) or in the various rubber solutions (6, 10, 13), is vulcanized in step f) at a pressure of 3 to 5 bar and/or a temperature of 60 to 170°C, preferably 90 to 150°C.