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    • 专利摘要:
    The invention relates to a method for modifying the surface of an elastomeric product having unsaturated carbon-carbon bonds, in particular a special glove, wherein the unsaturated carbon-carbon bonds in the region of the surface are at least partially saturated by a photochemi cal reaction with at least one thiol or by on the surface of the elastomer product at least partially a layer of a latex is surfaced or applied, whose unsaturated carbon carbon bonds in the region of its surface are at least partially saturated by a photochemical reaction with at least one thiol.
    公开号:AT513456A1
    申请号:T1086/2012
    申请日:2012-10-09
    公开日:2014-04-15
    发明作者:Armin Dr Holzner；Wolfgang Dr Kern；Dietmar Dipl Ing Lenko；Jakob Cornelius Dipl Ing Manhart；Raimund Dr Schaller；Sandra Dr Schlögl
    申请人:Semperit Ag Holding；
    IPC主号:
    专利说明:

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    J
    The invention relates to a method for modifying the surface of an elastomer having unsaturated carbon-carbon bonds, in particular a glove and an elastomer product, in particular glove, with unsaturated carbon-carbon bonds and having a surface.
    The modification of the surface of natural rubber gloves is already known from the prior art. For example, the surface is provided with coatings or roughened in order to achieve a better lubricity of the gloves. In particular, the attractability or the Nassanzannbarkeit the gloves should be improved. There are also functionalizations for reducing the allergy potential which adheres to natural rubber.
    The UV crosslinking of natural rubber via the thiol-ene reaction is also known from the prior art, for example from the documents AT 502 764 A1 and AT 508 099 A1 attributed to the Applicant.
    The present invention has for its object to provide an alternative way of surface modification of elastomer gloves or for modifying elastomer surfaces.
    This object is achieved, on the one hand, by saturating the unsaturated carbon-carbon bonds in the area of the surface at least partially by a photochemical reaction with at least one thiol or by at least partially applying a layer of a latex to the surface of the elastomer product , whose unsaturated carbon-carbon bonds in the region of its surface-2/44 N2011 / 25000
    At least partially by a photochemical reaction with at least one thiol are saturated or in the case of the elastomer product mentioned at the outset the unsaturated carbon-carbon bonds on the surface at least partially functionalized by -SR groups, wherein R represents at least one element selected from a group comprising H, vinyl compounds, acrylates, amines, amino acids (cysteine), acetylated amino acids (N-acetylcysteine), anhydrides, carboxylic acids, ethers , Epoxides, isocyanates, isothiocyanates, methacrylates, silanes, siloxanes, solid particles, polymer coatings.
    The advantage here is that the photochemical reaction proceeds via the thiol-ene reaction mechanism, so that a high efficiency of the reaction can be achieved with the method. In addition, this method is easily feasible with a relatively high reaction rate. Due to the photochemical activation, there is also the possibility that the saturation of the ethylenic double bonds takes place only in selective, predefinable subregions of the surface, whereby a conscious surface structuring in these areas can be achieved. In addition, the saturation of the elastomeric surface is reduced by the saturation of the ethylenic bonds. At the same time, it can also be used to improve the aging resistance of the elastomer. Another advantage of this method is the fact that this photochemical reaction proceeds at room temperature, so no heating is required.
    According to one embodiment variant of the process, it is provided that groups generated on the surface of the elastomer product by the reaction with the at least one thiol-free -SH groups. It can be created with this embodiment reactive sites on the elastomer surface. This makes it possible to further modify the thus prepared surface, for example, again via a thiol-ene reaction with a vinylic compound, in particular by a photochemical reaction mechanism. It is thus possible to increase the range of possible surface modifications, with the advantage that the connection of other substances to the elastomer surface is covalent, so that the adhesion is improved in comparison to 3/44 N2011 / 25000 • »
    • t lt · • · I · · · · · t «· ······· It is significantly better for purely adhesively bound substances. In particular, it can therefore be avoided that the substances bound to the surface are released during the use of the elastomer.
    Preferably used as the thiol is a mercapto compound selected from the group consisting of trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetramercaptoacetate, trimethylolpropane trimercaptoacetate, trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, propylene glycol-3 mercaptopropionate, ethoxylated trimethylolpropane tri-3-mercaptopropionate, polyol 3-mercaptopropionate, polyester 3-mercaptopropionate. These compounds are available, for example, from Bruno Bock Thio-chemicals and / or Sigma Aldrich. The use of these thiols has the advantage that a higher functionality is present so that anchor groups are available for further reactions. In addition, these compounds are non-toxic and non-carcinogenic.
    Preferably, the elastomeric product is used pre-crosslinked. It can thus be achieved a reduction of the chemicals used. On the other hand, however, an increase in production speed can be achieved as well. In addition, an increase in the hardness of the elastomer can be avoided, which may possibly occur due to steric hindrance in the mass of the elastomer.
    According to an embodiment variant, it is provided that the pre-crosslinking is likewise carried out photochemically. Thus, the advantage of the continuity of the methods used in the overall process for the production of the elastomer products is achieved.
    The reaction with the at least one thiol can be carried out on a solid surface of the elastomer product. This process variant is used in particular for the production of single-layer elastomer products, since it is thus possible to specifically modify surface regions of the elastomer. 4/44 N2011 / 25000
    • · • · *
    It can further be provided that the free -SH groups are reacted with at least one further chemical compound and / or with solid particles. Thus, within the scope of the invention, a further functionalization or a different functionalization-based on the surface modification by means of thiols-can be achieved, as a result of which the field of application of the elastomer products can be extended to a wide variety of different requirements.
    The further chemical compound can be selected from a group comprising or consisting of alkenes, acrylates, anhydrides, epoxides, isocyanates, isothiocyanates, methacrylates, thiols. With these compounds, the advantage is achieved that tailor-made anchor groups can be made available for various other reactions, including thermal reactions. It is thus possible to specifically change the surface polarity and the sliding friction properties of the elastomer product.
    Preferably, the solid particles are formed by inorganic particles. It can thus be achieved by reducing the contact surface of the elastomer with one hand, a reduction in tackiness or an improvement of Anziehbar-speed, in particular the Nassanziehbarkeit of gloves. In general, the adhesion of an elastomeric product to a surface due to this effect can be reduced. In addition, it is also possible that an additional functionality is introduced into the elastomer product via these solid particles, for example when moisture-absorbing solid particles are used.
    For a better attachment of the solid particles to the functionalized surface of the elastomer product, it is advantageous if the solid particles are also surface-functionalized before the reaction with the -SH groups.
    The functionalization of the solid particles can be carried out by generating free epoxy groups, mercapto groups, acrylate groups, anhydride groups, isocyanate groups, isothiocyanate groups, methacrylate groups, vinyl groups on the surface of the solid particles. By using this functional 5/44 N2011 / 25000 -5'- • · • ·
    Groups have the advantage that they can be covalently attached to the elastomer surface, whereby a lower risk of wound contamination and a lower allergy potential can be achieved. In addition, suitable for clean rooms suitable gloves can be provided.
    However, the functionalization of the solid particles can also be carried out with at least one chemical compound which is selected from a group comprising or consisting of silanes, siloxanes and carboxylic acids having functional groups, such as acrylate, anhydride, epoxy, isocyanate, isothiocyanate, Mercapto, methacrylate, vinyl groups. Examples of these are vinyltriethoxysilane, (3-glycidoxypropyl) trimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydrides, mercaptopropyltrimethoxysilane. These compounds are available from ABCR or Sigma Aldrich.
    In order to provide so-called "powder-free" elastomer products, in particular gloves, it is provided according to another embodiment that purely adhesively bound particles are removed from the surface of the elastomer product. It can thus reduce the allergy potential of the elastomer products. In addition, these adhesively bonded particles, which have a lesser effect in comparison to the covalently bound particles, may possibly be attributed to the production process.
    In addition to the embodiment of the method according to which the functionalization is carried out on a solid elastomer surface, there is also the possibility within the scope of the invention that the photochemical reaction with at least one thiol on a latex is carried out in the liquid phase and the latex is then applied to one, in particular pre-crosslinked, latex film is surfaced. This process variant is used in particular for the production of multilayer elastomer products. The advantage here is that with this process variant thiols can be covalently bonded not only in the area of the surface of a film but already on the individual latex particles, whereby an adjustment of the property potential of the elastomer product can be done. 6/44 N2011 / 25000 -6'- • · > ······ • 9 0 • · e
    It is also possible that the surface modification is carried out only in discrete areas of the elastomer product. It can thus be achieved a stronger structuring of the elastomer surface, whereby the lubricity of the elastomer product can be influenced. In addition, certain properties of the elastomeric product may be imparted by further covalently attaching further chemical compounds to the thiol groups in the modified regions.
    According to another variant of the method, it is provided that a polymer coating is applied to the surface of the elastomer product. Thus, this polymer coating can be covalently attached to the elastomer surface via the thiol groups, thereby achieving better adhesion of the polymer coating to the elastomer surface.
    For a better understanding of the invention, this will be explained in more detail with reference to the following figures.
    In part, in a schematically simplified representation:
    Fig. 1 shows the modification of NR latex films with vinyl-functionalized S1O2 particles;
    2 shows the structured exposure of polymers;
    3 shows the comparison of the IR spectra of untreated and TriThiol modified polyisoprene films.
    Fig. 4 shows the change in the contact angle of water by a surface functionalization using TriThiol.
    In the context of the invention, different approaches have been developed in order to reduce the tackiness of rubber films or to generally improve or change the properties of elastomer products.
    An elastomer product is understood in particular to be a glove, preferably a surgical glove or an examination glove. However, within the scope of the invention, other eggastomer products may also be used or processable or producible, such as catheters, condoms, (medical) balloons, teats , Respiratory masks, etc., or generally diving products, ie products that are usually produced by a dipping process.
    For the sake of completeness, it should be noted that an elastomer product in the context of the invention is understood as meaning a product of an elastomer which has unsaturated carbon-carbon bonds in the molecular structure, ie in particular ethylenic bonds (= diene rubber). Preferably, the elastomer is a natural rubber or a synthetic isoprene rubber. In addition, the invention is also applicable to other such unsaturated carbon-carbon bond-containing rubbers, particularly, in particular, homopolymers and copolymers such as nitrile-butadiene rubber, carboxylated nitro-butadiene rubber, polybutadiene, polychloroprene, styrene-butadiene rubber.
    The dipping method for producing elastomer products, in particular rubber gloves, has already been described in detail in the prior art. Usually, it comprises at least the following steps: providing a dip form, emergence of a coagulant, appearance of a latex. In addition, this dipping process includes various washing and drying steps. Usually, this dipping method is carried out continuously, for example in a so-called chain dipping system. For further details, reference is made to the relevant prior art. All embodiments of the invention have in common that the unsaturated carbon-carbon bond at least partially, preferably to, at least in the region of the surface of the elastomer product or of the elastomer (hereinafter referred to only as an elastomer, this reference also includes the elastomer product) at least approximately 2%, in particular between 3% and 75%, preferably between 4% and 10%, are saturated by reaction with a mercapto group.
    The mercapto group is provided in particular in the form of a thiol. Preference is given to using thiols which are selected from an 8/44 N2011 / 25000 -8'-
    Group comprising or consisting of trimethylolpropane tris-3-mercaptopropionate, 16-mercaptohexadecanoic acid, (11-
    Mercaptoundecyl) tetra (ethylene glycol), N-acetyl-L-cysteine, pentaerythritol tetramer-captoacetate, trimethylolpropane trimercaptoacetate, trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetra-3-mercaptopropionate, propylene glycol 3-mercaptopropionate, ethoxylated trimethylolpropane tri-3-mercaptopropionate, poly-ol 3-mercaptopropionate, polyester 3-mercaptopropionate.
    In addition to these preferably used chemical compounds having a mercapto group, it is also possible to use other such compounds within the scope of the invention, such as, for example, HS-R1R2R3, where R1 is represented by an element selected from the group consisting of alkyl, aryl, alkylaryl, A-rylalkyl, alkylarylalkyl, arylalkylaryl, silyl groups, R2 by an element selected from the group consisting of or consisting of acrylic, amino, amino acid, anhydride, carbonyl (C = O), carboxylic acid, carboxylate , - epoxy, hydroxy, isocyanate, isothiocyanate, methacrylic, mercapto, sulfonic acid, vinyl groups, R3 are formed by one element from the group consisting of or consisting of H, alkyl, aryl groups , Examples of these are poly (ethylene glycol) methyl ether thiol, 11-mercapto-1-undecanol, 16-mercaptohexadecanoic acid, cysteamine, cysteine, 2-propene-1-thiol, cis-9-octadecene-1-thiol.
    The use of multi-functional thiols, i. of chemical compounds having more than one mercapto group, such as the above-mentioned trimethylolpropane tris-3-mercaptopropionate has the advantage that free mercapto groups can be produced at least on the surface of the elastomer, on the further reaction with other chemical compounds to further Changing the properties of the elastomer product is made possible.
    In addition to the embodiment variant with chemical compounds having multiple homo-functionality, that is to say compounds having exclusively mercapto groups as functional groups in the molecule, it is also possible to use a polyfunctional chemical compound having hetero-functionality. 9/44 N2011 / 25000 -9 * - -9 * - • · · • · φ • * · φ ι • · φ ·
    ♦ · ··
    In addition to at least one mercapto group via which the connection of the compound to the elastomer surface takes place, these compounds have at least one further functionality, for example an amino group, a carboxylic acid group, an acrylate, anhydride, epoxy, isocyanate, isothiocyanate, methac -rylate, vinyl group, wherein mixed variants are possible, so that more than one of these groups in addition to the mercapto or the groups are present, for example a carboxylic acid group and an amino group or an ac-rylatgruppe with an anhydride, etc.
    In principle, there are two variants of the method. On the one hand, it is possible to carry out the functionalization with the at least one thiol-it is also possible to use mixtures of several different thiols-on a solid surface of the elastomer. On the other hand, there is the possibility that the functionalization takes place in the liquid phase of the latex, and then dipped a corresponding mold in the latex and thus the elastomeric article is produced.
    In the variant embodiment of the process on the solid surface of the elastomer, it is not absolutely necessary that the elastomer product is produced by a dipping process. All molding processes known from the prior art, for example injection molding, extrusion processes, compression molding, etc., are replaceable, although the dipping process in the context of the invention is the preferred process for producing the elastomer product. For the saturation or reaction of the unsaturated carbon-carbon bonds on a solid surface of an elastomeric product, for example an elastomeric film, the elastomer surface is brought into contact with the respective reagent. The elastomer is preferably used precrosslinked, wherein the pre-crosslinking is preferably carried out photochemically with a thiol, as described in the documents AT 502 764 A1 and AT 508 099 A1. In general, in the context of the invention, the pre-crosslinking is preferably carried out photochemically with a thiol. For the sake of completeness, it should be mentioned that other known crosslinking methods can also be used; for example, peroxide precrosslinking or salt bath crosslinking or crosslinking by means of actinic radiation can be carried out. Likewise, a sulfur crosslinking (at elevated temperature), as it is known in principle from the prior art, be carried out as a pre-crosslinking.
    The particular reagent, ie a mono- or polyfunctional thiol, is preferably used as an emulsion. In particular, an aqueous emulsion is used, and emulsions with organic solvents can in principle also be used.
    The concentration of the at least one thiol in the emulsion can be between 1% by weight and 20% by weight, in particular between 1% by weight and 10% by weight.
    In addition, the emulsion may also contain various adjuvants, e.g. Emulsifiers, for example TWEEN® 20, or stabilizers, antioxidants, dyes, antioxidants. The sum fraction of the emulsifier (s) added is preferably between 0.5% by weight and 5% by weight, based on the total mass of the emulsion.
    After the reaction is carried out photochemically, in particular at a wavelength or a wavelength spectrum in the visible and / or UV range, the emulsion is preferably also at least one photoinitiator added, for example Lucirin® TPO L. Further useful photoinitiators are in AT 502 764 A1 and AT 508 099 A1, to which reference is made in this regard.
    The total amount of the photoinitiator (s) added is preferably between 0.5 and 5% by weight, based on the total weight of the emulsion.
    If a water-soluble thiol is used, there is a possibility that it will be dissolved in the water. Likewise, pure liquid substances can be mixed in. 11/44 N2011 / 25000 ♦ · · · · · · · · · · · · · · · · · · · · · · · · · · ··· · · · ·
    be set. In this case, the cumulative amount of water-soluble thiol (s) is between 1% and 25% by weight.
    Commercially available dispersing equipment can be used to prepare the emulsion.
    The emulsion or the preparation with the at least one thiol is subsequently brought into contact with the elastomer, for example by immersing the elastomer in the emulsion. The temperature can be between 10 ° C and 70 ° C. Further, the duration of "wetting" can be between 0.1 minutes and 60 minutes. Thereafter, the wetted elastomer is dried.
    It is also possible that the wetting of the elastomer with the thiol preparation takes place in several steps, optionally with intermediate drying taking place between the individual steps.
    To form the covalent bonds between the elastomer and the at least one thiol, the wetted elastomer is exposed to a suitable radiation source, for example a UV radiation source, such as a UV radiation source. a Hg radiator (not doped or doped, for example with gallium or iron doped) or a laser.
    The irradiation dose may be between 0.2 J / cm 2 and 50 J / cm 2, especially between 0.5 J / cm 2 and 10 J / cm 2.
    The temperature can be between 10 ° C and 100 ° C.
    Optionally, the exposure may be performed in several steps, for example in two to eight repetitions.
    After exposure, the elastomer thus treated can still be washed, for example with water and / or an organic solvent, and / or dried. 12/44 N2011 / 25000 -12 »··» · »* · · · · ·
    * · · · I
    By this treatment of the elastomer, a reduction in stickiness, i. an increase in lubricity, and achieved an improvement in aging resistance.
    When using polyfunctional thiols, it is thus also possible to produce reactive groups on the surface of the elastomer, for example further thiol groups or amino groups or carboxylic acid groups, as has already been stated above. These reactive groups can be used to provide the functionalized elastomer with other chemical compounds that can react with these groups.
    Thus, according to one embodiment variant of the method, it is provided that the free -SH groups and / or the other reactive groups mentioned are reacted with at least one further chemical compound.
    The further chemical compounds can be selected from a group comprising thiols, epoxides and isocyanates. For example, a thermal linkage (it is generally a mixed variant of a photochemical with a thermal reaction possible) of thiols be carried out under disulfide formation. Epoxides can react under ring opening. By coupling other chemical compounds, a change in the surface polarity, increased aging resistance can be achieved by saturation of the C = C double bond or can thus be achieved a different surface reactivity.
    Depending on the reactants, this reaction can be carried out at a temperature between 10.degree. C. and 120.degree. C. and according to known reaction mechanisms. The duration of this reaction also depends on the particular concrete compounds which are reacted and can be between 1 minute and 90 minutes. Optionally, the reaction can be carried out under pressure or under vacuum. Likewise, actinic radiation is usable.
    With the method according to the invention, it is also possible solid particles, preferably large-scale available solid particles, in particular inorganic 13/44 N2011 / 25000 «· · · · · · · ·» «
    Nical solid particles, covalently, in particular exclusively covalently, to bind to the elastomer surface. These solid particles may preferably be selected from a group consisting of or consisting of sulfides, oxides, hydroxides, carbonates, borates, sulfates, phosphates, silicates, metal particles, e.g. Gold, silver, copper. In particular, the solid particles are selected from the group consisting of or consisting of chalk, diatomaceous earth, silica, kaolinites, quartz, amorphous silica, S1O2, calcite, T1O2.
    However, it is also possible for organic solid particles, for example at least partially consisting of starch or cellulose, to be covalently bonded to the elastomer surface.
    It is also possible to use cavities containing particles which are optionally loaded with an active substance, for example zeolites or cyclodextrins. Optionally, these particles may also be used for the adsorption of substances, e.g. Sweat, are used.
    Preferably, this attachment of solid particles to the elastomer surface also takes place photochemically under the conditions described above. The reaction itself can take place both in aqueous media and in liquid organic media. A possible schematic process sequence is shown in FIG. 1, wherein the solid particles shown are vinyl-functionalized SiO 2 particles.
    By this procedure, the advantage is achieved that a quantitative removal of non-covalently bound particles is possible because the stickiness of the elastomer surface is significantly reduced in the first step by the saturation of the unsaturated carbon-carbon bonds.
    In the specific case of Figure 1, a tri-functional thiol (TriThiol) was coupled to the NR surface via the UV initiated thiol-En reaction. This modification saturates most of the C = C double bonds and the film loses tack. Vinyl-functionalized SiO 2 compounds are added to the free SH groups via a second thiol-ene reaction via a second thiol-ene reaction. ## STR22 ## Particles bound to the surface.
    It is advantageous if the solid particles are surface-functionalized before the reaction with the -SH groups of the elastomer surface. This functionalization can be carried out, for example, by producing free epoxy groups, mercapto groups, acrylate groups, anhydride groups, isocyanate groups, isothiocyanate groups, methacrylate groups, vinyl groups, on the surface of the solid particles. In particular, a chemical compound selected from one of the preceding groups may be used for this purpose.
    The bonding of the solid particles to the elastomer surface can be carried out in accordance with the general procedure described above on the mercapto groups and / or further functional group on the elastomer surface, such as the above-mentioned functional groups, and in particular photochemically.
    However, it is also possible to thermally couple the solid particles to the elastomer surface, i. to bind covalently. For this purpose, preferably surface-modified solid particles are used with epoxy groups and / or amino groups. The preparation of these modified solid particles can be carried out by reacting the solid particles with the abovementioned compounds under the abovementioned conditions.
    The functionalized solid particles are suspended in water or an organic solvent. Thereafter, this suspension is brought into contact with the functionalized elastomer surface, for example by immersing the elastomer in the suspension. If necessary, this can be done several times.
    Subsequently, the thus treated elastomer is dried. The temperature may be selected from a range of 40 ° C to 150 ° C, in particular from a range of 40 ° C to 100 ° C. Drying may take place during a period of 15/44 N2011 / 25000 ····· ·· »-1 * 5 span between 5 minutes and 1000 minutes, especially between 10 minutes and 900 minutes. During drying, the thermal bonding of the solid particles to the elastomer surface takes place.
    It is also possible to thermally perform the above-mentioned further functionalization of the functionalized elastomer surface with at least one further chemical compound under these conditions.
    After the bonding, adhesively bound particles are preferably removed from the surface of the elastomer product, for example by washing and / or mechanically, for example by means of ultrasound.
    The solid particles used in the invention preferably have a particle size between 0.01 pm and 1000 pm, in particular between 0.1 pm and 10 pm.
    According to another variant of the method it is provided that the photochemical reaction with at least one thiol is carried out on a latex in the liquid phase and the latex is then applied to a, in particular precrosslinked, preferably photochemically precrosslinked, latex film.
    For this purpose, the at least one thiol is dissolved in a solvent, in particular water, whereby organic solvents can also be used. The at least one thiol may be selected from the thiols mentioned above. Preference is given to using N-acetylcysteine and / or cysteine and / or ethoxylated trimethylolpropane tri-3-mercaptopropionate.
    The amount of solvent is preferably such that, after the latex addition, a solids content of between 15% drc (dry rubber content) and 40% drc, in particular between 20% drc and 30% drc, is established.
    The proportion of the at least one thiol in the solution without latex can be between 0.5 phr and 50 phr, in particular between 1 phr and 20 phr. 16/44 N2011 / 25000 • ♦ ·· • · · · < «T ··· · T0- · * ♦ · · · · ♦ ♦ · * ♦ · * ·· ·
    In addition to the at least one thiol, the solution preferably also contains at least one photoinitiator. Possible photoinitiators are described in AT 502 764 A1 and AT 508 099 A1, to which reference is made in this regard.
    The sum fraction of the at least one photoinitiator can be selected from a range from 0.5 phr to 5 phr, in particular from a range from 1 phr to 2 phr, based on the latex.
    Dissolution of the ingredients of the solution without latex may be at a temperature between 10 ° C and 50 ° C and / or for a time between 0.5 minutes and 60 minutes.
    This solution is photochemically reacted with the added latex in the sequence, preferably with a wavelength or a wavelength spectrum from the visible and / or UV range. The radiation source can be selected from the radiation sources mentioned above.
    The irradiation dose may be between 0.2 J / cm 2 and 50 J / cm 2, especially between 0.5 J / cm 2 and 10 J / cm 2.
    The temperature can be between 10 ° C and 100 ° C.
    Optionally, the exposure may be performed in several steps, for example in two to eight repetitions.
    Before and / or after exposure, the treated latex may be further treated with other process chemicals, e.g. Anti-aging agents, stabilizers, Antiozonan-tien, defoamers, dyes, pigments, inorganic fillers, such. Chalk, be offset.
    For the production of an elastomer product, a first layer of an elastomer is subsequently produced in a first step, for example by a known dipping method, and precrosslinked, in particular photochemically precrosslinked. After at least one drying step and / or at least one washing step, the modified latex, which has been functionalized as described above, is used to form at least one further elastomer layer on the elastomers which have been produced at first 17/44 N2011 / 25000 ··· - λψ- ·· · «· • ·········). Thereafter, once again at least one drying and / or at least one washing step are carried out.
    According to another embodiment of the method, it is provided that the elastomer surface is at least partially provided with a polymer layer which is covalently bonded to the elastomer surface.
    In addition, in a first step, the functionalization of the elastomer surface is carried out with at least one thiol so that at least one type of the abovementioned functional groups (-SH, -COOH, -NH 2, epoxide, -NCO, -NCS) is present on the elastomer surface. The coupling itself can be carried out photochemically or thermally, as has already been explained above.
    The polymer layer can, for example, of a polyurethane or a silicone or a mixture of SBR with silicone or an acrylate or a siloxane or a polymer having functional groups, in particular alkenes, acrylates, anhydrides, epoxides, isocyanates, isothiocyanates, methacrylates, thiols to to achieve a covalent bond to the elastomer surface. Optionally, the polymers or monomers for forming the polymer layer can also be previously functionalized, in particular with at least one kind of the mentioned functional groups.
    The functional groups on the polymer may be present as side groups or terminal.
    Preferred polymers are silicones, polyurethanes, urethane acrylates, acrylates, polyisocyanates, polyester polyols, vinyl polymers, diene elastomers. Examples include Desmophen® 1652, Synthomer VL 11005, Desmolux® XP 2740, Bayhydrol® UV XP 264, Desmolux® VP LS 2299, available from Bayer or Synthome.
    Suspensions or solutions are again produced from the optionally functionalized polymers or monomers or oligomers (for functionalization, the respective reagent can be added to this suspension) or the polymer is used as the pure substance. At least one polymer may be allowed to react at least 18/44. N2011 / 25000 ··············································································
    Emulsifier and / or at least one photoinitiator are added. The concentrations can be selected according to the above information.
    This suspension is subsequently applied to an especially precrosslinked, preferably photochemically precrosslinked, elastomer, in particular surfaced, optionally dried, and then exposed, for which purpose the abovementioned radiation sources and irradiation parameters can be used.
    Applied monomers or oligomers or the polymers can also be crosslinked after the connection to the elastomer surface.
    In principle, there is the possibility that the entire surface of the functionalized elastomer is provided with at least one further chemical compound and / or with solid particles and / or with the polymer coating.
    According to one embodiment variant, however, it may be provided that the at least one further chemical compound and / or the solid particles and / or the polymer coating are formed or arranged only in discrete regions on the elastomer surface. In order to achieve this, the region of the elastomer surface which is not further functionalized can be covered with the radiation source with a corresponding mask, as shown in FIG. 2, so that in a subsequent washing step the non-photochemically reacted and thus not covalently bound Substances are washed off.
    According to a non-preferred embodiment, there is the possibility that the at least one further chemical compound and / or the solid particles and / or the suspension for the polymer coating is already applied only in discrete areas.
    The mask may be a mechanical mask or a chemical mask or an optical mask. A chemical mask is understood as meaning a substance which, prior to the application of the respective suspensions or emulsions or 19/44 N2011 / 25000 -19 '· · · < Solution is applied to the non-coated areas, for example, painted.
    In addition to the pure surface structuring, it is thus also possible, for example, to achieve a permanent application of information on the elastomer product, for example the glove size in the case of elastomer gloves.
    Although in the foregoing only the at least partial, preferably complete, saturation of the unsaturated carbon-carbon bonds of the elastomer has been treated, it is in principle also possible, although not preferred, for the unsaturated carbon-carbon bonds within the elastomer to be at least partially photochemically saturated with at least one thiol become.
    With the exception of the first described variant of the method, in all other methods according to the invention a functionalization of the functionalization, i. the functionalized elastomer surface, performed. The functional groups arranged on the surface as a result of the first functionalization act as anchor groups for the further functionalization.
    The photochemical coupling of the at least one thiol to the elastomer surface takes place after the thiol-ene reaction.
    With the method according to the invention elastomeric products can be produced which have a better lubricity and a better aging resistance compared to an untreated elastomer. In addition, properties such as e.g. Wettability, polarity, sliding friction are influenced or the elastomeric product completely new properties are imparted, such. textured elastomer surfaces, odor, color, look and feel. Depending on the choice of thiol, the elastomer surface may be given polar or nonpolar properties.
    To evaluate the covalent bond between the elastomer and the thiol, TriThiol was chosen as the model substance and a polyisoprene. Pro-20/44 N2011 / 25000 -20-ben were analyzed by infrared spectroscopy. Fig. 3 shows a recorded spectrum.
    It can be concluded from the results of infrared spectroscopy that the incorporation of the tri-thiol is effected via a covalent bond to the elastomer surface, since the C = C double bonds (831 cm -1) decrease as a result of the modification. In addition, the modified elastomer surfaces detect IR bands at 2430 cm-1 and 1735 cm-1 due to the tri-thiol.
    Further contact angle measurements were made on tri-thiol modified NR latex films. The result is shown in FIG.
    The incorporation of the tri-thiol enhances both the polar and the dispersed energy portion of the surface energy of the polyisoprene surface - i. the wettability and the polarity of the surface increase, as can be seen from the following table.
    Thiol concentration [wt%] Polar energy fraction [mN / m] Dispersed energy fraction [mN / m] Total surface energy [mN / m] 0 1.0 34.6 35.6 1.5 4.7 34.5 39 , 2 5 3,6 36,2 39,8 10 2,7 43,9 46,8
    As can be seen from FIG. 4, the contact angle of 105 ° of the untreated NR latex decreases to 80 ° with 5% by weight of tri-thiol or 71 ° with 10% by weight of tri-thiol.
    In general, with the method according to the invention, a reduction of the contact angle to water by at least 10%, based on the untreated elastomer surface, can be achieved. By using N-acetylcysteine, the polarity of the elastomer surface can even be almost doubled (Re- 21/44 reduction of 105 ° untreated NR latex film to 54 ° at 5% by weight N-acetylcysteine).
    Interestingly, it was found that the contact angle increases again when using 10% by weight of N-acetylcysteine (74 °).
    It was further found that the covalent attachment of solid particles decreases the polarity again (modification with vinyl-functionalized S1O2 particles: water contact angle 91 °).
    In other words, the method of the invention can thus provide elastomers having "tailored" polarities on the surface. Thus, the reactivity of the elastomer surface is adjusted accordingly.
    Measurements were made according to Owens DK, Wendt RC. Estimation of the surface free energy of polymers. J Appl Polym It was 1969; 13 (8): 1741-1747 and Rabel W. Wetting theory and its application to the study and use of the surface properties of polymers. Paint and varnish. 1971; 77 (10): 997-1006.
    The modified surfaces were also characterized by zeta potential measurement. For unmodified natural rubber surfaces, the isoelectric point (ξ = 0) is 3.45, indicating a weakly negatively charged surface. Inert polymer surfaces, such as e.g. Although polypropylene has an isoelectric point (ξ = 0) of 3.8-4.1, the proteins, phospholipids, and other organic impurities can shift to the acidic region on the NR surface.
    Functionalization with TriThiol (SH-functionalized surface) gives an isoelectric point (IEP) of 3.0, indicating a more negatively charged surface. This value is comparable to OH-functionalized surfaces, which also have an IEP in the range of 3.0. The covalent bonding of the vinyl particles to the mercapto groups again gives the film the properties of an inert surface. This could be confirmed by zeta potential measurement, because the IEP shifts from 3.0 to 3.9. With vinyl 22/44 N2011 / 25000 99 ♦ · 9 9 9 • '«
    ····················································································································································
    Particles functionalized sample was characterized in a duplicate assay. In both measurements, a congruent IEP was obtained, indicating covalent binding of the particles.
    Subsequently, with the help of tribological measuring methods with a Linea rtribometer according to B. Bhushan, Modern tribology handbook. CLC Press, Boca Raton, London, New York, Washington D.C. 2001, the sliding friction coefficient of particle modified NR surfaces determined and compared with the characteristics of commercial surgical gloves. The results in the following table show that the sliding friction properties of particle modified surfaces are in the range of powdered NR surfaces.
    Comparison of the sliding friction coefficients of selected NR surfaces
    Sample description Sliding friction coefficient State of the art Glove with chlorinated inside m ~ 0.31 State of the art Glove with coated inside m - 0.22 State of the art Glove with powdered inside m ~ 0.50 Vinyl particle modified NR surface m ~ 0.55 - 0.77
    In the following, some non-limiting examples are given in the course of working out the invention. 23/44 N2011 / 25000 • i 2 2 2 2 · · · · · · · · · · · · · · · · · · · · ·
    The chemicals used for the examples are summarized in Table 1.
    Table 1: Materials and chemicals used Chemical Manufacturer Structural formula, specification
    Aktisil® MM Hoffmann Mercapto-modified SiCV particles (dso = 2.2
    Mineral pm)
    Aktisil® VM 56 Hoffmann Vinyl-modified SiO 2 particles (ds0 = 2.2 pm)
    mineral
    TWEEN® 20 Sigma Aldrich HOH ^ o
    Sigma Ald-rich
    Lucirin® TPO-L
    Genocure® DM HA
    Irgacure® 2959 N-acetylcysteine L-cysteine
    Sigma Ald-rich Sigma Ald-rich
    O
    OH nh2 24/44 N2011 / 25000
    Trimethylolpropane tris-3-mercaptopropionate (TriThiol) Bruno Bock Chemische Fabrik GmbH Co KG O 0 HS O-ν -O SH -'X ^ Y ^ / SH 0 Bayhydrol® UV XP 2649 Bayer urethane acrylate dispersion Bayhydrol® UV XP 2740 Bayer Acrylate Dispersion Styrene butadiene Redispersible polymer dispersion Poly (mercaptopropyl) ABCR methylsiloxane
    Example 1: Modification of a Dried Film Surface, Coupling of Tri-Functional Thiol Derivatives (Generation of Free SH Groups)
    In the photochemical coupling of tri-thiol via thiol-ene reaction, the following steps are carried out:
    Preparation of an aqueous emulsion with 10% by weight of trithiol, 1.1% by weight of TWEEN 20 and 1% by weight of Lucirin TPO L Dispersion of the emulsion by means of dispersing apparatus (Ultraturax) for 5 minutes at room temperature Fixing of a UV precrosslinked NR latex film in a Petri dish with adhesive tape • Pour over the elastomer film with the aqueous emulsion • Remove the film from the Petri dish after 10 minutes
    • Dry the sample for 1 min at 100 ° C. • Expose sample with Hg emitter (Fusion UV) (parameter: see Table 2) 25/44 N2011 / 25000
    Table 2: Exposure equipment parameters (Fusion UV) for SH functionalization
    settings
    device parameters
    Runs Lamp Type Lamp Power Conveyor Speed Irradiation Dose_ 1 -4
    Mercury radiator (non-doped and Ga-doped) 40% - 60% 3.5 m / min - 6 m / min 0.5 J / cm2 - 25 J / cm2 - • 10 min in fluorination. and 10 min in ethanol with stirring (magnetic stirrer) wash • Then functionalized sample for 10 min at 100 ° C dry
    Example 2: Modification of a Dried Film Surface, Coupling of Monofunctional Thiol Derivatives (Generation of Free NH 2 and COOH)
    Groups)
    In the photochemical coupling of N-acetylcysteine or cysteine via thiol
    In a reaction, the following steps are carried out:
    Preparation of an aqueous emulsion containing 1-10% by weight of N-acetylcysteine or cysteine, 1.1% by weight of TWEEN 20 and 1% by weight of Lucirin TPO L
    The further steps are carried out analogously to Example 1.
    Example 3: Photochemical modification of the liquid phase
    In the photochemical coupling of N-acetylcysteine or cysteine via thiol
    The following steps are carried out in the reaction: • Dissolve process chemicals (1-2 phr Irgacure, 1 - 20 phr L-cysteine or N-acetylcysteine) in deionized water while stirring at elevated temperature. Amount of water so that after NR-latex addition, a solids content of 30% drc. established. • Add process chemical solution to a pre-vulcanized NR latex. • Stir the mixture at RT for 2h with magnetic stirrer 26/44 N2011 / 25000 Transfer 16 ml of the mixture to a glass petri dish (1mm layer thickness). Mix with Hg emitter or Ga doped Hg emitter (Fusion UV) (parameters: see Table 3)
    Table 3: Equipment parameters of the exposure unit (Fusion UV) for the modification of latex
    Device parameters Settings Runs 1-4 Lamp type Mercury radiator (non-doped and Ga-doped) Lamp power 40% - 60% Conveyor speed 3.5 m / min - 6 m / min Irradiation dose 0.5 J / cm2 - 25 J / cm2 • Alternatively, the UV exposure can also be carried out in the falling film reactor. • Mix mixture with 0.5 phr Ralox (anti-aging agent). • Stir the mixture at RT for 2 h with magnetic stirrer
    The corresponding latex films are produced in a two-layer dipping process: • Surfacing of a precrosslinked NR latex onto a porcelain form (20 s at RT)
    • 0 s - 15 s dry at 120 ° C • Emergence of the modified NR latex (30 s at room temperature RT (about 20 ° C)
    • 60 s - 90 s dry at 120 ° C • Wash in FhOdeion. at 80 ° C for 60 s
    • Dry for 15 min at 120 ° C • Wash in FhOdeion. at 80 ° C for 60 s
    • Dry for 5 min at 120 ° C 27/44 N2011 / 25000 -27- ····· • · · · · · · · ·
    Example 4 Photochemical Coupling of Inorganic Particles, Performance in Aqueous Systems
    In the course of photochemical coupling of inorganic S1O2
    Macroparticles are performed following process steps:
    Preparation of an aqueous suspension with 0.015 wt .-% - 0.5 wt .-% Vi-nyl-resp. -SH modified SiO 2 macro particle, 0.15% by weight - 0.7% by weight of TWEEN 20 and 1.7% by weight of Genocure DMHA • Dispersion of the suspension in an ultrasonic bath for 10 minutes - 20 minutes at room temperature • Fixing of an -SH-functionalized NR latex film (See Example 1) in a Petri dish. • Pour the elastomer film over the aqueous suspension. • Remove the film from the Petri dish after 2 minutes
    • Dry the sample for 10 min at 70 ° C • Exposure sample with Hg (Fusion UV) (See Table 3) • Wash exposed film for 16 h at room temperature in water • Film for 10 min - 15 min at 70 ° C dry
    Example 5: Photochemical Coupling of Inorganic Particles, Carrying out in Organic Solvents • Preparation of a Suspension with 0.015% by Weight-0.2% by Weight of Vinyl- or -SH-Modified SiO 2 Macroparticles and 1.7% by Weight Lucirin TPO-L in toluene • Dispersing the suspension in an ultrasonic bath for 10 min at room temperature • Pouring over the elastomer film lying in a Petri dish with the suspension. Float the film with tweezers. • Remove the film from the Petri dish after 2 minutes
    • Dry the sample for 10 min at 70 ° C • Exposure sample with Hg (Fusion UV) (See Table 3) • Wash exposed film for 16 h at room temperature in toluene • Film for 10 min - 45 min at 70 ° C dry 28/44 N2011 / 25000 -28- • ···· ··· ···· • ··· ··································· · · ·· ··· ·
    Example 6: Thermal Coupling of Inorganic Particles, Performance in Aqueous Systems
    In the course of the thermal coupling of inorganic SiCV macro particles, the following process steps are carried out: Preparation of an aqueous suspension with 0.015% by weight 0.5% by weight of epoxy-modified SiO 2 macro particles. Dispersion of the suspension with dispersing device (Ultraturax) for 10 min at room temperature and then in an ultrasonic bath for 10 min at room temperature • Fixing an SH-functionalized NR latex film (see above) in a Petri dish • Pour the elastomer film over the aqueous suspension • Remove the film from the Petri dish after 2 min
    • Dry the sample for 10 min - 900 min at 40 ° C - 100 ° C • Wash the film for 16 h at room temperature in water • Dry the film for 10 min - at 70 ° C for 45 min
    EXAMPLE 7 Thermal Coupling of Inorganic Particles, Carrying out in Organic Solvents Preparation of a Suspension with 0.015% by Weight 0.2% by Weight of Epoxy-Modified SiO 2 Macroparticles in Toluene Dispersion of the suspension in an ultrasonic bath for 10 minutes Room temperature • Pour the elastomer film over the aqueous suspension. Prevent the film from floating with tweezers. • Remove the film from the Petri dish after 2 min
    • Dry the sample for 10 min - 900 min at 40 ° C - 100 ° C • Wash film for 16 h at room temperature in toluene • Dry film for 10 min - 70 ° C for 15 min 29/44 N2011 / 25000 -29- • · • · · ··· -29- • · • · · · · · ·
    • · · ······ ······ • · · · · · · · · · · ·
    Example 8: Photochemical Coupling of Polymer Coatings
    In the course of the photochemical coupling of selected polymer coatings, the following process steps are carried out: The polymer coatings: a) Bayhydrol® UV XP 2649 (urethane acrylate dispersion) b) Redispersed styrene-butadiene dispersion (40% by weight in yeast.) C) Bayhydrol® UV XP 2740 (acrylate dispersion) d) poly (mercaptopropyl) methylsiloxane are admixed with 1% by weight of lucirin TPO L and optionally with 1% by weight to 5% by weight of tri-thiol (emulsified with 1.1% by weight Tween 20 in HfeOdeion.) And with a dispersing unit (Ultraturax). The coatings are surfaced on precrosslinked and SH-functionalized (See Example 1) NR latex films (15 s - 45 s at room temperature)
    • Dry the coatings for 15 min at 70 ° C • Exposure sample with Hg emitter (Fusion UV) (parameters: see Table 4)
    Table 4: Equipment parameters of the exposure unit (Fusion UV) for the Ankopp k £ i2J / on_Pol | 2TTerbeschichüjnc | en ^^ __ <ii <ii ^ _e ^ _ ^ _ i ^ _i ^^^ _ ee ^ _i _ ^ _ i
    Device parameters Settings Cycles 1-3 Lamp type Mercury lamp (not doped) Lamp power 30% - 40% Conveyor belt speed 3 m / min - 6 m / min Irradiation dose 0.5 J / cm2- 25 J / cm2 30/44 N2011 / 25000 • · • · • ··························································································································· ······ ··· ·
    Example 9: Thermal Coupling of Polymer Coatings
    For the thermal coupling of polymer coatings, the coupling reactions of polymer coatings on photochemically modified surface summarized in Table 5 were carried out.
    Table 5: Thermal coupling of polymer coatings on photochemically modified elastomer surfaces - surface as dried modified NR surface photochemically modified Polymer coating thermally coupled substance class -SH polymers with epoxy groups -SH polymers with mercapto groups -COOH Polymers with epoxide groups
    The embodiments show possible embodiments of the invention. 31/44 N2011 / 25000
    权利要求:
    Claims (20)
    [1]
    -1 -

    1. A process for modifying the surface of an elastomeric product having unsaturated carbon-carbon bonds, in particular a glove, characterized in that the unsaturated carbon-carbon bonds in the region of the surface are at least partially saturated by a photochemical reaction with at least one thiol or by at least partially surfacing or applying to the surface of the elastomer product a layer of a latex whose unsaturated carbon-carbon bonds in the region of its surface are at least partially saturated by a photochemical reaction with at least one thiol.
    [2]
    2. The method according to claim 1, characterized in that are generated by the reaction with the at least one thiol-free -SH groups on the surface of the elastomer product.
    [3]
    3. Process according to claim 1 or 2, characterized in that the thiol used is a chemical compound selected from a group comprising trimethylolpropane tris-3-mercaptopropionate, pentaerythritol tetra ramercaptoacetate, trimethylolpropane trimercaptoacetate, trimethylolpropane tri-3-mercaptopropionate, pentaerythritol tetraacetate. 3-mercaptopropionate, propylene glycol-3-mercaptopropionate, ethoxylated trimethylolpropane tri-3-mercaptopropionate, poly-3-mercaptopropionate, polyester-3-mercaptopropionate.
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the elastomeric product is used pre-crosslinked.
    [5]
    5. The method according to claim 4, characterized in that the pre-crosslinking is carried out photochemically. 32/44 N2011 / 25000 -2- ·· · • · · · · ·············································································
    [6]
    6. The method according to any one of claims 1 to 4, characterized in that the reaction is carried out with the at least one thiol on a solid surface of the elastomer product.
    [7]
    7. The method according to any one of claims 2 to 7, characterized in that the free -SH groups are reacted with at least one further chemical compound and / or with solid particles.
    [8]
    8. The method according to claim 7, characterized in that the further chemical compounds are selected from a group comprising alkenes, acrylates, anhydrides, epoxides, isocyanates, isothiocyanates, methacrylates, thiols.
    [9]
    9. The method according to claim 7, characterized in that the solid particles are formed by inorganic particles.
    [10]
    10. The method according to claim 7 or 9, characterized in that the solid particles are surface functionalized before the reaction with the -SH groups.
    [11]
    11. The method according to claim 10, characterized in that the functionalized functionalization of the solid particles by generating free epoxy groups, mercapto groups, acrylate groups, anhydride groups, isocyanate groups, isothiocyanate groups, methacrylate groups, vinyl groups, is carried out on the surface of the solid particles.
    [12]
    12. The method according to claim 10, characterized in that the functionalization of the solid particles is carried out with at least one chemical compound which is selected from a group comprising silanes, siloxanes and carboxylic acids having functional groups, such as acrylate, anhydride, epoxy , Isocyanate, isothiocyanate, mercapto, methacrylate, vinyl groups. Examples are vinyltriethoxysilane, (3-glycidoxypropyl.) Examples of these are vinyltriethoxysilane, (3-glycidoxypropyl ) trimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydrides, mercaptopropyltrimethoxysilane.
    [13]
    13. The method according to any one of claims 7 to 11, characterized in that adhesively bound particles are removed from the surface of the elastomer product.
    [14]
    14. The method according to any one of claims 1 to 5 or 6 to 12, characterized in that the photochemical reaction is carried out with at least one thiol on a latex in the liquid phase and the latex is then applied to a, in particular precrosslinked, latex film.
    [15]
    15. The method according to any one of claims 1 to 13, characterized in that the surface modification is carried out in discrete areas of the elastomer product.
    [16]
    16. The method according to any one of claims 1 to 14, characterized in that on the surface of the elastomer product, a polymer coating is applied.
    [17]
    17. Elastomer product, in particular glove, having unsaturated carbon-carbon bonds and having a surface, characterized in that the unsaturated carbon-carbon bonds on the surface are at least partially functionalized by single or multiple functional -SR groups, where R is at least one element selected from a group comprising H, vinyl compounds, acrylates, amines, amino acids (cysteine), acetylated amino acids (N-acetylcysteine), anhydrides, carboxylic acids, ethers, epoxides, isocyanates, isothiocyanates, methacrylates, silanes, siloxanes , Solid particles. 34/44 N2011 / 25000 ······················································································· # · · · · · ···· * _ 4 - ······ ··· ·
    [18]
    18. Elastomer product according to claim 17, characterized in that at least partially a polymer coating is covalently bonded to the elastomer product via the -SR groups.
    [19]
    19. Elastomer product according to claim 17 or 18, characterized in that this is formed at least two layers.
    [20]
    20. Elastomer product according to one of claims 17 to 19, characterized in that the -SR groups are arranged only in discrete areas of the surface. Semperit Aktiengesellschaft Holding

    Lawyer GmbH 35/44 N2011 / 25000
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    AT502764B1|2005-09-12|2010-11-15|Semperit Ag Holding|MIXTURE AND METHOD FOR PRODUCING A NETWORKED ELASTOMER AND DEVICE FOR PRODUCING A DIVING ARTICLE|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA1086/2012A|AT513456B1|2012-10-09|2012-10-09|Process for modifying the surface of an elastomer product|ATA1086/2012A| AT513456B1|2012-10-09|2012-10-09|Process for modifying the surface of an elastomer product|
    US14/047,541| US9894946B2|2012-10-09|2013-10-07|Method for modifying the surface of an elastomer product|
    PL13187837T| PL2719720T3|2012-10-09|2013-10-09|Method for modifying the surface of an elastomer product|
    EP13187837.3A| EP2719720B1|2012-10-09|2013-10-09|Method for modifying the surface of an elastomer product|
    HUE13187837A| HUE025536T2|2012-10-09|2013-10-09|Method for modifying the surface of an elastomer product|
    ES13187837.3T| ES2550579T3|2012-10-09|2013-10-09|Procedure for surface modification of an elastomer product|
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