• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a method for bonding particles to the surface of an elastomer, in particular a glove, wherein the surface of the elastomer is at least partially epoxidized and the particles are covalently bonded to the epoxy groups after the epoxidation of the elastomer surface.
    公开号:AT513457A1
    申请号:T1087/2012
    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:

    ······ ···· · · · · · · · · mA ··· ·· ♦ ··
    The invention relates to a method for attaching particles to the surface of an elastomer, in particular a glove, wherein the surface is at least partially epoxidized, and an elastomer product.
    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.
    For the modification of the surface of natural rubber, the epoxidation of the rubber surface is known from the prior art.
    Thus, US Pat. No. 7,442,746 A describes a process for the synthesis of an epoxidized polymer which comprises the following steps: (1) preparation of a cationically stabilized polymer latex with at least one conjugated diolefin monomer in a first stage, (2) treatment of the polymer latex from step (1) with Formic acid or acetic acid and hydrogen peroxide, and (3) reacting the mixture for a predetermined time and at a predetermined temperature to achieve the desired degree of epoxidation.
    From DE 102 60 219 B is known that it is by dipping a rubber product in or by coating with a treatment liquid which is prepared by addition of hydrogen peroxide and other additives, such as surfactant, alcohol, thickening agent, another (further) composition for lowering - 2/34 N2012 / 09700 •••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••• aqueous acetic acid or formic acid solution, it is possible to epoxidize the surface layer of the rubber product, thereby imparting non-sticky, non-sticky, and other barrier properties to this surface, without the occurrence of toxic gases and without powder dust contamination occurs during the manufacturing process, and without compromising the properties inherent in the rubber product, such as elasticity, elongation and tensile strength to be (worsened).
    GB 1396090 A describes a process for producing an article comprising contacting an alkyl hypohalite or halo-substituted alkyl hypohalite with a molded article of a rubber having ethylenic double bonds and bonding a coating or other rubber, metal or wood to the treated surface of the molding. The bonding can be done with the help of an Epoyx binder.
    US 5,310,819 A describes superficially epoxidized elastomeric articles in which the ethylenic bonds of the elastomer are saturated by immersing the articles in an epoxidation solution for a sufficient time.
    From US 5,804,318 A improved lubricating coatings for reducing the friction coefficients of the surfaces of medical devices are known. The lubricious hydrogel coatings are covalently bonded to the epoxide-functionalized surfaces.
    US 6,797,783 A describes a natural rubber obtained by modifying a deproteinized natural rubber having a nitrogen content of less than 0.10% by weight, the modification comprising epoxidizing the deproteinized natural rubber with trifluoroperacetic acid. 3/34 N2012 / 09700
    ··· «· · · · · · · ······
    The present invention has for its object to provide a way to surface-modification of elastomer gloves or to modify elastomer surfaces.
    This object is achieved, on the one hand, by the particles being covalently bonded to the epoxide groups after the epoxidation in the case of the aforementioned process or, in the case of the elastomer product mentioned at the beginning, having the surface at least partially covalently bound to the elastomer particles.
    The advantage here is that an improvement in the lubricity of the elastomer products is achieved by the covalently bonded to the elastomer particles. The attractability, in particular the wet suitability, of elastomer gloves can thus be improved. The covalent attachment ensures that the property improvement or change is maintained by the surface modification over a longer period of time. In addition, with the particles, the elastomer product may be given additional functionality if the particles are chosen appropriately, for example when using particles loaded with active ingredients. The binding of the particles via epoxide groups has the advantage that the epoxidation of the elastomer surface can be carried out thermally, ie no actinic radiation is required for the preparation of the surface. In addition, unreacted epoxy groups on the surface of the elastomer reduce its tackiness and can improve the aging resistance by at least partially saturating the ethylenic groups of the elastomer.
    Preferably, the particles are formed by inorganic particles. It can thus be achieved a reduction in tackiness or an improvement in the attractability, in particular the Nassanziehbarkeit of gloves by the contact surface of the elastomer is reduced with one hand. In general, the adhesion of an elastomeric product to a surface due to this effect can be reduced. In addition, however, it is also possible that an additional functionality in the elastomer product is introduced via these solid particles. N2012 / 09700 ······················································································· • For example, when moisture-absorbing solid particles are used.
    For better attachment of the solid particles to the functionalized surface of the elastomer product, it is advantageous if the solid particles are also functionalized on the surface before the reaction.
    The functionalization of the solid particles can be carried out by producing free mercapto groups and / or free amino groups and / or carboxylic acid groups and / or epoxy groups and / or hydroxyl groups and / or anhydride groups and / or isocyanate groups and / or isothiocyanate groups on the surface of the solid particles. By using these functional groups, the advantage is achieved that anchor groups with high reactivity for the attachment of the solid particles to the elastomer surface are available.
    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 acrylate groups, anhydride groups, isocyanate groups, isothiocyanate groups, methacrylate groups, vinyl groups. By using these functional groups, the advantage is achieved that anchor groups can be provided for the coupling of further functional compounds to the solid particles.
    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 particles, which have a lesser effect compared to the covalently bound particles, may possibly be recycled into the production process. It is thus avoided wound contamination with particles when using the elastomer product in the medical field. The elastomer product is also suitable for use in clean rooms. 5/34 N2012 / 09700 •
    The epoxidation of the elastomer 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. In addition, by avoiding bulk epoxidation, the aging properties of the elastomer can be improved.
    In addition to this variant of the method, the possibility also exists within the scope of the invention for the epoxidation to be carried out on a latex in the liquid phase. This process variant can be used for the production of multilayer elastomer products. The advantage here is that with this process variant if necessary, the epoxidation can not only be done in the area of the surface but already on the individual latex particles, whereby an adjustment of the property potential of the elastomer product can be done.
    It is also possible that the epoxidation is carried out only in discrete areas of the elastomer. It can thus be achieved a stronger structuring of the elastomer surface, whereby the lubricity of the elastomer can be influenced. In addition, specific properties of certain areas of the elastomer can be imparted.
    Preferably, the particles have a particle diameter between 10 nm and 10 pm. With particles below 10 nm, although an effect is observed, but this is insufficient in terms of improving the lubricity of the elastomer. With particle sizes of more than 10 pm, it could be observed that the improvement in the bond to the elastomer surface decreases again due to the size of the particles.
    According to another embodiment, it can be provided that the particles are at least partially crosslinked with each other. This can be done, for example, via unreacted functional groups on the surface of the particles. It can thus be achieved a "net-like" structure. In addition, liability may be limited to the following: 6/34 N2012 / 09700 • ··············································· ····································································································································································································································
    The particles can have at least one active substance, whereby the spectrum of the functionalization of the elastomer surface can be significantly increased. Optionally, a post-loading of the particles can be carried out, whereby the service life of the elastomer product can be extended.
    For a better understanding of the invention, this will be explained in more detail with reference to the following figure.
    It shows in a schematically simplified representation:
    Fig. 1 shows the modification of NR latex films by epoxidation and subsequent attachment of amino-functionalized SiO 2 particles.
    An elastomer product is understood in particular to be a glove, preferably a surgical glove or an examination glove. However, in the context of the invention, other elastomer products can also be replaced or processed or produced, such as catheters, condoms, (medical) balloons, teats, respiratory masks, etc., or generally immersion articles, ie products which are usually produced by means of 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-forming rubbers, especially 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, encountering 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 2%, in particular between 10% and 80%, are saturated by epoxidation.
    In principle, there are two variants of the method. On the one hand, it is possible to carry out the epoxidation on a solid surface of the elastomer. On the other hand, there is the possibility that the epoxidation takes place in the liquid phase of the latex, and then a corresponding mold is immersed 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., can be used, although the dipping process within the scope 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, such as an elastomeric film, the elastomeric surface is contacted with the respective reagent, for example immersed in or sprayed with the epoxidation reagent. The elastomer is preferably used precrosslinked, the precrosslinking preferably being carried out photochemically with a thiol, 8/34 N2012 / 09700 ····························································································· ♦ · · ♦ ♦ · ♦ ···
    As described in 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. However, all other types of precrosslinking, for example sulfur crosslinking or peroxidic crosslinking or generally crosslinking by means of actinic radiation, are also possible within the scope of the invention.
    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 reagent for epoxidizing the elastomer may, for example, be an aliphatic or aromatic peracid, e.g. Peracetic acid, performic acid, trifluoro-peracetic acid, permaleic acid, perbenzoic acid, monoperphthalic acid, o-sulfoperbenzoic acid, p-nitroperbenzoic acid and m-chloroperbenzoic acid, the former being preferred. The concentration of the peracid may be between 1 wt .-% and 41 wt .-%, in particular between 2 wt .-% and 4 wt .-%, remainder water (with hydrogen peroxide and carboxylic acid (s)) amount. Commercially available peracids are used.
    However, other epoxidizing agents can be used, such as hydrogen peroxide in acidic or alkaline medium or tertiary butyl hydroperoxide in alkaline medium, or it can be the epoxidation of the elastomer according to any of the prior art documents referred to hereinbefore , be performed. Likewise, epoxidation with catalysts is possible, e.g. Metal Salen Complex + NaOCI (Jacobsen Epoxidation) or Shi Catalyst + Oxone (Shi Epoxidation).
    It is also possible the in situ formation of peracids by reaction of a carboxylic acid with H2O2, e.g. the in situ formation of performic acid.
    The temperature at which the treatment with the epoxidation reagent is carried out may be between 30.degree. C. and 70.degree. C., in particular between 40.degree. C. and 50.degree .. N2012 / 09.700 Μ ··· ········· · · · · · · ·····································
    •. Furthermore, the duration of the "wetting" can be between 1 minute and 400 minutes, in particular between 40 minutes and 100 minutes. Thereafter, the wetted elastomer, e.g. for a period of between 30 seconds and 5 minutes, are immersed in water to rinse off excess epoxidation reagent.
    Finally, the wetted elastomer is dried at a temperature of between 20.degree. C. and 100.degree. C., in particular between 55.degree. C. and 70.degree. Preferably, the drying takes place within a time period between 10 minutes and 100 minutes, in particular between 15 minutes and 30 minutes.
    It is also possible that the wetting of the elastomer with the Epoxidierungsreagens takes place in several steps, optionally between the individual steps an intermediate drying takes place.
    As a result of the epoxidation, the ethylenic double bonds on the surface of the elastomer are at least partially u.a. reacts to an oxirane ring. These oxirane rings are subsequently available for covalent attachment of the particles to the elastomer as functional groups.
    According to another process variant, it is provided that the epoxidation is carried out on a, optionally precrosslinked, latex in the liquid phase. This latex is then formed into the elastomer product, for example dipped. If appropriate, the latex can be applied to a, in particular precrosslinked, preferably photochemically precrosslinked, latex film for producing an elastomer product which is at least two-layered. For this procedure, a suspension of the latex is prepared. For stabilization of this suspension, at least one stabilizing agent, for example a Polyethylenglycolnonylphenylether, e.g. Synperonic® NP 30, can be added. The stabilizer can be dissolved in water and then added directly to the latex or latex without further addition of water. The sum proportion of the at least one stabilizing agent can be between 2 phr and 15 phr (parts per hundred parts rubber). 10/34 N2012 / 09700 • · • • • • • · * 10 ················································································································
    The latex may have a solids content between 20% drc (dry rubber content) and 60% drc.
    The latex can be used at a temperature between 20 ° C and 60 ° C.
    As a result, the suspension can be acidified, wherein preferably a pH between 2 and 5, in particular between 3 and 4, is set. For pH adjustment, a carboxylic acid, in particular acetic acid, is preferably used. However, other acids may also be used, for example inorganic acids such as HCl. It is also possible to use a buffer. Suitable buffer substances are sodium, potassium, calcium or magnesium formate, acetate or butyrate, sodium dihydrogen phosphate, disodium hydrogencarbonate or sodium, potassium, calcium or magnesium carbonate, with sodium carbonate being preferred.
    The epoxidation reagent can either be added to this suspension or generated in situ in it. For the former variant it is preferred to use again a peracid, in particular peracetic acid, other acids, e.g. as stated above, can be used. The peracid is used in particular as an aqueous solution with a concentration between 1 wt .-% and 41 wt .-%.
    More preferably, an amount of peracid is added such that a ratio of the molar concentration of peracid to the molar concentration of polyisoprene units of the elastomer is between 0.04 and 0.7.
    By direct addition of the peracid, the concentration may be between 4 mol% and 70 mol%, based on the isoprene units.
    In the case of in situ preparation of the peracid, the concentration of the carboxylic acid may be between 10 mol% and 120 mol%, that of H2O2 between 10 mol% and 120 mol%, based in each case on the isoprene units. 11/34 N2012 / 09700 • · • • • • • • * 11 ·· • t ··· · • ·
    As described above, for the in situ generation of the epoxidation reagent, an oxidizing agent, in particular hydrogen peroxide, and a carboxylic acid, in particular formic acid or acetic acid, are added to the suspension. The oxidizing agent and the carboxylic acid may be added in equimolar amounts.
    The carboxylic acid can be used, in particular as an aqueous solution, with a concentration between 20% by weight and 60% by weight.
    The oxidizing agent can be used, in particular as an aqueous solution, with a concentration between 25% by weight and 50% by weight.
    It is particularly preferred to add an amount of oxidizing agent and carboxylic acid such that a ratio of the concentration of the peracid produced therefrom, in particular performic acid, to the concentration of polyisoprene units of the elastomer is between 0.1 and 0.3.
    The liquid phase epoxidation may be carried out at a temperature between 20 ° C (room temperature) and 80 ° C and / or for a period between 20 minutes and 60 hours.
    The epoxidation of the latex particles is terminated by neutralization, for example with a 10% strength by weight potassium hydroxide solution.
    From this suspension prepared in this way, the elastomer product is produced, in particular by dipping a mold.
    Optionally, the shaping can be carried out in several steps, for example in two to eight repetitions.
    Before and / or after epoxidation, the treated latex may be further treated with other process chemicals, e.g. Anti-aging agents, stabilizers, Antiozonan-tien, defoamers, dyes, inorganic fillers such. Chalk, be offset. 12/34 N2012 / 09700 • · · · · · · · · · · · · · · · · · · · · · * * *···· * V «• · · · 12 · * * ·· · ··· ··································
    To produce an elastomer product which is at least two-layered, 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. Optionally, after at least one dry and / or optionally at least one washing step, at least one further elastomer layer is applied, in particular surfaced, to the first elastomer layer produced from the modified latex which has been functionalized as described above. Thereafter, once again at least one drying and / or at least one washing step are carried out.
    On the, in particular according to one of the two process variants, epoxidized, i. Particles which are provided with epoxide groups are subsequently applied to the elastomer, these particles being covalently bonded to the elastomer surface via the epoxide groups with ring opening.
    In particular, inorganic solid particles, preferably industrially available solid particles, are used. Preferably, these particles are selected from the 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, SiO 2, calcite, TiO 2.
    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.
    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 advantageous if the solid particles are surface-functionalized prior to attachment to the Epo-xigruppen the elastomer surface. These are the items that you will want to remember • • • • • • • • • • • • • ft
    Functionalization can be carried out by forming free mercapto groups and / or free amino groups and / or anhydride groups and / or isocyanate groups and / or isothiocyanate groups and / or hydroxy groups on the surface of the solid particles. In particular, a chemical compound selected from a group comprising 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatepropyltrimethoxysilane, hydroxymethyltriethoxysilane, and the like can be used thereto. These compounds are available from ABCR or Sigma Aldrich and Evonik Industries, respectively.
    It should be mentioned in this connection that the functionalized solid particles are at least mostly commercially available, e.g. Hoffmann Mineral or Sigma Aldrich or Evonik Industries.
    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 anhydride, epoxy, isocyanate, isothiocyanate, mercapto groups. Examples of these are (3-glycidoxypropyl) trimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydrides, mercaptopropyltrimethoxysilane. These compounds are available from ABCR or Sigma Aldrich.
    The mercapto group is provided in particular in the form of a thiol. Thiols are preferably used for this purpose, which are selected from a group comprising or consisting of trimethylolpropane tris-3-mercaptopropionate, 16-mercaptohexadecanoic acid, (11-
    Mercaptoundecyl) tetra (ethylene glycol), N-acetyl-L-cysteine, pentaerythritol tetramer-capoacetate, 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. These connections 14/34 N2012 / 09700 3 ·· «·························································································· For example, Bruno Bock Thiochemicals and / or Sigma Aldrich are available.
    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, iso-thiocyanate, methacrylic, mercapto, sulfonic acid, vinyl groups, R3 are formed by one element from the group consisting of or consisting of H, alkyl, aryl groups ,
    The amino group is provided in particular in the form of primary amines. Amines are preferably used for this purpose, which are selected from a group comprising or consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane.
    In the context of the invention, however, it is also possible to use non-functionalized particles, in particular if they are already provided with functional groups due to the chemical structure.
    For functionalization, the at least one thiol and / or amine and / or anhydride and / or isocyanate and / or isothiocyanate and / or the compound with the hydroxy groups in a solvent, in particular water, wherein organic solvents can be used, is dissolved. The concentration of the at least one thiol and / or amine and / or anhydride and / or isocyanate and / or isothiocyanate and / or the compound with the hydroxy groups and / or with the at least one chemical compound selected from the group consisting or consisting from silanes, siloxanes and carboxylic acids having functional groups such as anhydride, epoxy, isocyanate, isothiocyanate, mercapto groups can be between 0.1 wt .-% and 50 wt .-%, in particular between 15/34 N2012 / 09700 0.5% by weight and 15% by weight, based in each case on the total weight with the (inorganic) particles.
    In this solution, the respective particles are given for functionalization in the sequence.
    The functionalization of the solid particles can be carried out at a temperature between 0 ° C and 200 ° C and / or for a duration between 5 minutes and 720 minutes and / or at a pH between 3 and 6. Preferably, the functionalization takes place with stirring.
    The reaction itself can be carried out both in aqueous media and in liquid organic media, for example ethanol, toluene, cyclohexane, hexane, isopropanol. A possible schematic process sequence is shown in FIG. 1, wherein amino-functionalized SiO 2 particles are used as 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.
    The functionalized particles are suspended in water or an organic solvent. The suspension is preferably used with a concentration between 0.01% by weight and 10% by weight, in particular between 0.01% by weight and 1% by weight, of amino group (n) and / or mercapto group ( n) - and / or carboxylic acid group (s) and / or epoxy group (s) and / or hydroxyl group (s) and / or anhydride group (s) and / or isocyanate group (s) and / or isothiocyanate group (s) -modified particles produced by means of commercial dispersing equipment. 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. It is also possible that the elastomer is only partially immersed. In the case of multiple dives, this partial dive should be limited to one or more dive steps, whereby it is also possible here that only partial immersion takes place during all dive steps.
    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. The drying can be carried out for a period between 5 minutes and 1000 minutes, in particular for a period between 10 minutes and 900 minutes. During drying, the covalent attachment of the solid particles to the elastomer surface occurs.
    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 10 nm and 10 pm, in particular between 20 nm and 50 nm or between 1 pm and 5 pm.
    In principle, there is the possibility that the entire surface of the epoxidized elastomer with at least one type of particles - it can also at least two different types of particles, for example, both quartz and zeolite, are used in order to achieve a different property profile of the elastomer - provided becomes.
    According to one embodiment variant, however, it can be provided that the particles are arranged only in discrete regions on the elastomer surface. In order to achieve this, the region of the elastomer surface which is not to be further functionalized can be covered with a corresponding mask so that the non-covalently bound particles are washed off in a subsequent washing step.
    According to one embodiment, there is the possibility that the particles are already applied only in discrete areas. 17/34 N2012 / 09700 17 • ·
    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 is applied to the areas not to be coated prior to application of the respective suspensions or emulsions or solution, for example by brushing on.
    It is likewise possible for the epoxidation of the elastomer to be carried out only in the areas to be provided with the particles, for which purpose corresponding masks, as stated, can also be used.
    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.
    According to a further embodiment, it can be provided that the particles are at least partially crosslinked with each other after the covalent attachment to the surface of the eggastomer.
    This cross-linking can be achieved via unreacted functional groups of the functionalized particles described above, optionally using an additional reagent which reacts with these functional groups and thus establishes a bond between the particles.
    However, it is also the use of polyfunctional thiols and / or amines or and / or anhydrides and / or isocyanates and / or isothiocyanates, i. of chemical compounds having more than one mercapto and / or amino or carboxylic acid group and / or epoxy group and / or hydroxyl group and / or anhydride group and / or isocyanate group and / or isothiocyanate group, for example trimethylolpropane tris-3-mercaptopropionate possible, with which free mercapto groups can be produced at least on the surface of the previously epoxidized elastomer, via which a further reaction with other chemical compounds for further modification of the properties of the elastomer product is made possible. 18/34 N2012 / 09700
    1" ·· · ·· ···
    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. In these compounds, for example, besides at least one mercapto group via which the connection of the compound to the particle surface takes place, at least one further functionality is present, for example an amino group, a carboxylic acid group, an epoxide group, a hydroxy group, an anhydride group, an isocyanate group, an isothiocyanate group a vinyl group, wherein mixed variants are also possible, so that more than one of these groups are present in addition to the mercapto or the mercapto groups, for example a carboxylic acid group and an amino group.
    When using polyfunctional thiols or polyfunctional amines or polyfunctional polycarboxylic acids, polyalcohols, polyacetals it is also possible to produce reactive groups on the surface of the particles, for example further thiol groups or amino groups or carboxylic acid groups.
    It is also possible to use polymers with functional groups (alkenes, acrylates, anhydrides, epoxides, isocyanates, isothiocyanates, methacrylates, thiols) to modify the particles in order to achieve a covalent bond to the elastomer surface. The polymers can be used in dispersion, in solution and as pure substance.
    The functional groups may be present as side groups or terminal.
    The reactive groups can be used to provide the functionalized particles with other chemical compounds that can react with these groups.
    The further chemical compound can be selected from a group comprising acrylates, amines, amino acids (cysteine), acetylated amino acids (N-acetylcysteine), anhydrides, carboxylic acids, ethers, epoxides, isocyanates, isothiocyanates, 19/34 N2012 / 09700
    T9 nate, methacrylates, silanes, siloxanes. It is thus achieved an additional improvement of the Gleitreibungseigenschaften or can be introduced another functionality (for subsequent reactions).
    Depending on the reactants, this reaction can be carried out at a temperature between 20.degree. C. and 80.degree. C. and according to known reaction mechanisms. The duration of this reaction also depends on the particular specific compounds which are reacted and can be between 1 minute and 100 minutes. Optionally, the reaction can be carried out under pressure or under vacuum.
    According to another embodiment of the invention, it is provided that the functional groups on the particle surface, which are not required for the covalent attachment to the elastomer, are covalently bonded at least in regions to a polymer layer.
    The polymer layer can be made, for example, from a polyurethane or a silicone or from a mixture of SBR with silicone or an acrylate or a siloxane or from a polymer having functional groups, in particular alkenes, acrylates, anhydrides, epoxides, isocyanates, isothiocyanates, methacrylates, thiols, alcohols , Carboxylic acids. 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.
    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, polyvinyl alcohol, polyacrylic acid, available from Bayer and Synthome, respectively.
    Suspensions are again produced from the optionally functionalized polymers or monomers or oligomers (for functionalization, the respective reagent can be added to this suspension), at least one of which has at least one of these 20/34 N2012 / 09700 20 ••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••••
    Emulsifier and / or at least one photoinitiator, if the monomers or oligomers are photochemically crosslinked, can be added.
    The particles may also be used to provide thereon and / or at least one active ingredient. Possible agents are e.g. Antiperspirants, antibacterial agents, fungicides, fragrances, skin care agents, e.g. a vitamin or aloe vera, pigments, agents to change the water absorption behavior, stabilizers, etc ..
    It is with the method 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.
    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. a skin care effect, the water absorption behavior, etc. are influenced or the elastomer product completely new properties are imparted, such. textured elastomer surfaces, odor, color, look and feel.
    It was using tribological measurement methods with a linear tribometer 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 elastomer surfaces are in the range of powdered NR surfaces.
    Comparison of the sliding friction coefficients of selected NR surfaces 21/34 N2012 / 09700
    Sample description Sliding friction coefficient m State of the art glove with chlorinated inner surface m ~ 0.31 State of the art glove with coated inner side m ~ 0.22 State of the art glove with powdered inner surface m ~ 0.50 NR surface modified with amino-functionalized SiO 2 particles m ~ 0.7
    In the following, some non-limiting examples are given in the course of working out the invention.
    The chemicals used for the examples are summarized in Table 1.
    Table 1: Materials and chemicals used
    Chemicals Manufacturer Structural formula, Specification Aktisil AM Hoffmann Mineral Amino-modified SiO 2 particles (d50 = 2.2 pm) Aktisil MM Hoffmann Mineral Mercapto-modified SiO 2 particles (d 50 = 2.2 pm) Nanoparticles Sigma Aldrich Amino-modified SiO 2 particles (dso = 20 nm) peracetic acid conc. (39%) Sigma Aldrich 22/34 N2012 / 09700
    formic acid
    Sigma Aldrich H202 Synperonic NP 30
    Sigma Aldrich Sigma Aldrich
    1. Modification of the Dried Film Surface 1.1 Epoxidation with peracids
    In the epoxidation of NR films, the following steps were carried out: washing the dried latex film in deionized water (10 min at RT = room temperature, = 20 ° C.) epoxidizing the washed latex film in an aqueous peracetic acid solution (2 wt. ) at 40 ° C for 40 min. • Brief immersion of the epoxidized latex film in deionized water (1 min at RT). • Drying at 70 ° C for 15 min. 1.2 Epoxidation of the liquid phase 1.2.1 Epoxidation with peracids
    During the epoxidation of the liquid NR latex, the following steps were carried out: stabilization of the NR latex with Synperonic NP 30 (10 phr) and adjustment of the solids content of 20-60% by weight latex is brought to a pH of 3 with acetic acid - 4 acidified • Optional addition of peracetic acid (39% solution), molar concentration ratio is: 23/34 N2012 / 09700 • ♦ Μ ··· «- = 0.07-0.5 [olyisoprene unit] or 0.07 Mol% to 0.5 mol% peracetic acid based on the isoprene units or in situ formation of performic acid by H2O2 and formic acid with a molar concentration ratio of: M [hcooh] β2 10 [olyisoprene unit] [olyisoprene unit]
    Reaction temperature 21 ° -60 ° C. reaction time until 3 ° -48 h termination of the reaction by neutralization with a KOH solution (10% by weight)
    For example, 4g Synperonic can be dissolved in 33.2g H 2 O at 40 ° C and added to 67g NR (60% drc). This approach is stirred for 15 hours. It is then acidified to pH ~ 4 and 28.44 g of HCOOH (98-100%) and 33.26 g of H 2 O 2 (30%) are slowly added. 2. Preparation of epoxidized NR latex films
    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)
    • dry for 0 - 15 s at 120 ° C • emergence of the epoxidized NR latex (30s at RT)
    • Dry for 20 min at 120 ° C • Peel off the film 3. Coupling of inorganic particles 24/34 N2012 / 09700 • · • · · ♦ • · · · · · «· · · · · ·····« • · · · · · 24 ..... • · ···························
    Example 1: Performance in aqueous systems
    In the course of the coupling of inorganic SiCV macro particles, the following process steps were carried out: Preparation of an aqueous suspension with 0.015-0.5% by weight of commercially available amino- or mercapto-modified SiCV macro particles by weighing the particles in H 2 O deionized 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 epoxidized NR latex film in a Petri dish • Pour over the elastomer film with the aqueous suspension • Remove film from the Petri dish after 2 min
    • Dry the sample for 10 - 900 min at 40 - 100 ° C • Wash the film for 16 h at room temperature in water • Dry the film for 10 - 15 min at 70 ° C
    Example 2: Carrying out in organic solvents Preparation of a suspension with 0.015-0.2% by weight of amino- or mercapto-modified SiCV macro-particles in toluene Dispersion of the suspension in an ultrasonic bath for 10 minutes at room temperature Pouring over of the elastomer film with the suspension Preventing the film from floating with tweezers • Remove the film from the Petri dish after 2 minutes
    • Dry the sample for 10 - 900 min at 40-100 ° C. • Wash the film for 16 h at room temperature in toluene. • Dry film at 70 ° C for 10 - 15 min
    Example 3 Coupling of Nanoscale Particles Preparation of a Suspension with 0.015-0.05% by Weight of Amino-Modified SiO 2 Nanoparticles (Suspended in Ethanol) in Toluene 25/34 N2012 / 09700 * 23 · · · · · · · · • Disperse the suspension in an ultrasonic bath for 30 min at room temperature. • Pour the elastomer film over it Suspension, prevent the film from floating with tweezers. • Remove the film from the Petri dish after 2 minutes
    • Dry the sample for 10 - 900 min at 40 - 100 ° C • Wash the film for 16 h at room temperature in toluene • Dry the film at 70 ° C for 10 - 15 min
    On an industrial scale, the implementation of the method can be carried out, for example, directly on a chain dipping system by immersing the gloves on the mold in the particle dispersion. For this purpose, it is advantageous if the particles are at least temporarily dispersed in the corresponding immersion basin, preferably constantly, and the spent particles are replenished. The thermal coupling can take place during the drying or optionally vulcanization (in the case of S-vulcanised gloves) of the gloves in the oven. Subsequently, the elastomer products can be washed with water to remove unbound particles.
    Alternatively, the particles may also be applied by immersing the gloves (on the mold) in particle lashes 26/34 N2012 / 09700
    权利要求:
    Claims (15)
    [1]
    Anspruch [en] A process for bonding particles to the surface of an elastomer, in particular a glove, wherein the surface of the elastomer is at least partially epoxidized, characterized in that the particles covalently attached to the epoxide groups after epoxidation of the elastomer surface.
    [2]
    2. The method according to claim 1, characterized in that particles are used as inorganic particles.
    [3]
    3. The method according to claim 1 or 2, characterized in that the particles are surface-functionalized before the reaction.
    [4]
    4. The method according to claim 3, characterized in that the functionalized functionalization of the particles by generating free mercapto groups and / or free amino groups and / or carboxylic acid groups and / or epoxy groups and / or hydroxyl groups and / or anhydride groups and / or isocyanate groups and / or Isothiocyanate groups, is carried out on the surface of the particles.
    [5]
    5. The method according to claim 3 or 4, characterized in that the functionalization of the particles is carried out with at least one chemical compound which is selected from a group comprising 3-aminopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, hydroxymethyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3 Glycidoxypropyltrimethoxysilane, 3- (triethoxysilyl) propylsuccinic anhydride.
    [6]
    6. 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. 27/34 N2012 / 09700 2 • • • • • • ο ····································· •·····································
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the epoxidation of the elastomer is carried out on a solid surface.
    [8]
    8. The method according to any one of claims 1 to 6, characterized in that the epoxidation is carried out on a latex in the liquid phase.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the epoxidation is carried out in discrete regions of the elastomer.
    [10]
    10. Elastomer product, in particular glove, with a surface, in particular produced by a process according to one of claims 1 to 9, characterized in that the surface has at least partially covalently bonded to the elastomer particles.
    [11]
    11. Elastomer product according to claim 10, characterized in that this is formed at least two layers.
    [12]
    12. Elastomer product according to claim 10 or 11, characterized in that the particles are arranged only in discrete areas of the surface.
    [13]
    13. Eiastomerprodukt according to claim any one of claims 10 to 13, characterized in that the particles have a particle diameter between 10 nm and 10 pm.
    [14]
    14. Elastomer product according to one of claims 10 to 13, characterized in that the particles are at least partially crosslinked with each other. 28/34 N2012 / 09700
    [15]
    15. Elastomer product according to one of claims 10 to 14, characterized in that the particles have at least one active ingredient.

    Lawyers c & r & Partner Rechtsanwalt GmbH Semperit Aktiengesellschaft Holding by 29/34 N2012 / 09700
    类似技术:
    公开号 | 公开日 | 专利标题
    AT513457B1|2015-05-15|Elastomer product with covalently bound particles
    DE102012214888A1|2013-02-28|Process for treating carbon fibers, fiber-reinforced resins and processes for producing the fiber-reinforced resins
    EP1999164B1|2009-10-28|Nanofillers, nanocomposites composed of an organic binder and nanofillers, process for their production and their use
    DE1467440B2|1974-05-09|Process for the production of reinforced moldings from elastomers
    EP1221457A2|2002-07-10|Process to modify the functionality of organofunctional substrate surfaces
    EP2719720B1|2015-08-12|Method for modifying the surface of an elastomer product
    EP3423514B1|2020-09-02|Method for producing a prophylactic article
    AT511292B1|2013-01-15|GLOVE
    EP3423515B1|2020-08-26|Method for producing a prophylactic article
    DE10260219B4|2008-11-13|Process for the surface treatment of a rubber product
    DE102015200277B4|2019-10-10|Use of an adhesion promoter for the cohesive connection of a polymeric organic material with an inorganic substrate and method for the cohesive connection of a polymeric organic material with an inorganic substrate using an adhesion promoter
    KR100721880B1|2007-05-28|Method for coating two component typed urethane paint comprising nano silver
    AT518300B1|2020-02-15|Method of making a prophylactic article
    DE1646152C3|1975-04-30|Process for the preparation of a coating of a mercaptohydrocarbyl silicon compound
    EP0239531B1|1990-01-03|Production of sealant assembly
    EP0001775A1|1979-05-16|Method of making adhesive-repellent coatings based on polysiloxane, and their application in the coating of paper
    DE102010060355B4|2022-01-13|Rubber mixture and its use for the manufacture of a tyre, belt, strap or tube
    DE1234382B|1967-02-16|Process for firmly bonding rubber to metals
    DE102015211519A1|2016-12-29|bonding agent
    DE2451706A1|1976-05-06|SURFACE PRE-TREATMENT OF METALLIC OR OXIDIC SURFACES
    DE3504241A1|1986-08-14|Bis[|benzyl]oligosulphides, and mixtures containing these and structurally related, oligomeric siloxanes
    DD244754A1|1987-04-15|PROCESS FOR PRODUCING SURFACE-COATED SEAMLESS LATEX DOWELING ARTICLES
    同族专利:
    公开号 | 公开日
    EP2719710A1|2014-04-16|
    AT513457B1|2015-05-15|
    US20140096308A1|2014-04-10|
    US9290632B2|2016-03-22|
    ES2569736T3|2016-05-12|
    PL2719710T3|2016-10-31|
    HUE027626T2|2016-11-28|
    EP2719710B1|2016-03-09|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US6903165B2|2001-05-14|2005-06-07|Daicel Chemical Industries, Ltd.|Process for producing epoxidized diene polymer|
    US20060074185A1|2004-09-27|2006-04-06|Sivapackia Ganapathiappan|Latex particulates with epoxide functional groups|
    US20070049659A1|2005-08-25|2007-03-01|Quay Jeffrey R|Functionalized alumina particles for polymer composites|
    US20090136746A1|2005-08-30|2009-05-28|Catalysts & Chemicals Industries Co., Ltd.|Composite Polymer, Thermosetting Coating Composition, and Molded Article|
    GB1396090A|1974-03-14|1975-05-29|Nippon Zeon Co|Surface modification of rubber articles|
    DD296853A5|1989-01-16|1991-12-19|Friedrich-Schiller-Universitaet Jena,De|METHOD FOR PRODUCING SURFACE-FUNCTIONALIZED TRAWER MATERIALS|
    US5310819A|1992-01-23|1994-05-10|The United States Of America As Represented By The Secretary Of The Navy|Surface epoxidation of elastomers|
    US6797783B1|1995-05-24|2004-09-28|Kao Corporation|Modified natural rubber|
    US5804318A|1995-10-26|1998-09-08|Corvita Corporation|Lubricious hydrogel surface modification|
    JP3643912B2|2002-04-01|2005-04-27|株式会社レヂテックス|Rubber product surface treatment method|
    US6972148B2|2003-06-23|2005-12-06|Kimberly-Clark Worldwide, Inc.|Glove having improved donning characteristics|
    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|
    JP2007205234A|2006-02-01|2007-08-16|Denso Corp|Fuel injection valve|
    US7442746B2|2006-10-19|2008-10-28|The Goodyear Tire & Rubber Company|Epoxidation of unsaturated cationically stabilized polymer latex|
    AT508099B1|2009-03-17|2015-07-15|Semperit Ag Holding|METHOD FOR PRODUCING A NETWORKED ELASTOMER|JP6337693B2|2014-08-26|2018-06-06|信越化学工業株式会社|Silane coupling agent aqueous solution, method for producing the same, and surface treatment agent|
    US10154699B2|2015-09-10|2018-12-18|Ansell Limited|Highly chemical resistant glove|
    AT518357B1|2016-03-04|2018-09-15|Semperit Ag Holding|Method for producing a prophylactic article|
    AT518307B1|2016-03-04|2020-04-15|Semperit Ag Holding|Method of making a prophylactic article|
    JP6409106B1|2017-08-30|2018-10-17|太陽インキ製造株式会社|Curable resin composition, dry film, cured product and printed wiring board|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA1087/2012A|AT513457B1|2012-10-09|2012-10-09|Elastomer product with covalently bound particles|ATA1087/2012A| AT513457B1|2012-10-09|2012-10-09|Elastomer product with covalently bound particles|
    US14/047,588| US9290632B2|2012-10-09|2013-10-07|Elastomer product with covalently bonded particles|
    ES13187847.2T| ES2569736T3|2012-10-09|2013-10-09|Elastomer product with covalently bound particles|
    HUE13187847A| HUE027626T2|2012-10-09|2013-10-09|Elastomer product with covalently bonded particles|
    EP13187847.2A| EP2719710B1|2012-10-09|2013-10-09|Elastomer product with covalently bonded particles|
    PL13187847.2T| PL2719710T3|2012-10-09|2013-10-09|Elastomer product with covalently bonded particles|
    [返回顶部]