• 专利附录
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    • 专利摘要:
    The invention relates to a process for producing a prophylactic article, in particular a glove, from a (carboxylated) diene rubber, after which at least one layer of a (carboxylated) diene latex is applied to a mold and the (carboxylated) diene latex is crosslinked with a crosslinking agent, which is immobilized on inorganic and / or organic particles to form modified particles and the modified particles are added to the (carboxylated) diene latex.
    公开号:AT518357A1
    申请号:T50175/2016
    申请日:2016-03-04
    公开日:2017-09-15
    发明作者:Dr Holzner Armin；Dr Kern Wolfgang；Ing Jakob Cornelius Manhart Dipl；Sahin Melahat；Ing Dr Raimund Schaller Dipl；Dr Schlögl Sandra
    申请人:Semperit Ag Holding；
    IPC主号:
    专利说明:

    The invention relates to a process for producing a prophylactic article, in particular a glove, from a (carboxylated) diene rubber, after which at least one layer of a (carboxylated) diene latex is applied to a mold, and the (carboxylated) diene latex is crosslinked with a crosslinking agent.
    The invention further relates to a prophylactic article, in particular glove, comprising a layer of a (carboxylated) diene elastomer, wherein the (carboxylated) diene elastomer chains of the (carboxylated) diene elastomer are covalently crosslinked via organic molecules and ionically via metal cations.
    Moreover, the invention relates to the use of inorganic and / or organic particles on which a crosslinking agent is immobilized to form modified particles.
    Prophylactic articles, such as, in particular, surgical and examination gloves, are usually made from an elastomeric latex by immersion in hand-shaped dip forms. On the dipping forms a film, from which subsequently the finished disposable glove is formed by vulcanization or crosslinking of the latex.
    Natural latex prophylaxis products have a relatively high allergy potential. For this reason, more and more synthetic latices are used for the preparation of prophylactic articles. But even these are not entirely hypoallergenic, as they may still contain allergens from the manufacturing process, such as powders to improve the attractability, or process chemicals, such as crosslinking chemicals or crosslinking accelerators.
    In order to address these problems, the prior art has already proposed processes for the production of prophylactic articles with reduced allergy potential.
    For example, WO 2011/068394 A1 describes a method according to which a carboxylated nitrile butadiene is added to a methacrylic acid and ZnO. As a result, this mixture obtains self-crosslinking properties, so that sulfur-containing crosslinkers and accelerators can be dispensed with. However, this composition still contains the heavy metal Zn, so that a certain potential for allergen testing remains. Similarly, US 2010/0152365 A1 describes the use of a car-boxylated nitrile-butadiene copolymer to make a glove by dipping. Again, ZnO is used for ionic crosslinking.
    To adjust certain mechanical properties of elastomeric gloves made of XNBR, it is known to add fillers to the latex. For example, H. Mohd. Ghazaly et al, "Some Factors Affecting Dipped Nitrile Latex Films", J. Rubb. Res., 4 (2), 88-101, discloses the use of fumed silica and silane-modified silica, wherein it is stated in this publication that no significant changes in film-forming properties could be detected by the use of silane-modified silica. For crosslinking either sulfur or ZnO is used.
    From Tutchawan Siriyong and Wirunya Keawwattana, "Utilization of Different Curing Systems and Natural Zeolites as Fillers and Absorbent for Natural Rubbers / Nitrile Rubber Blend", Kasetsart J. (Nat. Sei.) 46: 918-930 (2012) It is known that the use of zeolite in NR / XNBR blends increases tensile strength and 100% modulus. The crosslinking is carried out by conventional sulfur vulcanization or by peroxidic crosslinking. The sulfur systems showed the greatest increase in tensile strength. Of the
    Zeolite is used as a sorbent to increase the oil resistance of the rubber product. For this application, peroxide crosslinking gives the best results. With regard to the preparation of prophylactic articles, in particular gloves, sulfur crosslinking is to be preferred on the basis of the results in this publication, in particular the increased tensile strength, because of their thinness. The increase in the 100% modulus, however, speaks against the use of these results in the manufacture of gloves, as it reduces the wearing comfort.
    It is also known to modify the surface of natural rubber gloves to reduce its allergy potential. For example, Applicant's US 2014/0096307 A1 describes a process for modifying the surface of an elastomer having unsaturated carbon-carbon bonds which, at least in part, are saturated by at least one thiol by a photochemical reaction. For saturation, solid particles, i.a. Zeolite particles which are covalently bound to the surface of the glove. This modification of the glove surface takes place after immersing the carrier layer of the natural rubber by applying the particles to the surface of the carrier layer. In the finished glove, the particles are thus on the inside of the gloves, as they are turned after diving to peel off. Similarly, US 2014/0096308 A1, also assigned to the Applicant, describes, inter alia. the attachment of zeolite particles to a natural rubber glove via epoxide groups.
    The present invention has for its object to provide an improved prophylactic article.
    The object is achieved in the method mentioned above in that the crosslinking agent is immobilized on inorganic and / or organic particles to form modified particles and the modified particles are added to the (carboxylated) diene latex.
    Furthermore, the object of the invention is achieved by the above-mentioned prophylactic article, in which the metal cations are part of inorganic particles, and the organic molecules are immobilized on the inorganic particles.
    Finally, the object of the invention is achieved by the use of inorganic and / or organic particles on which a crosslinking agent is immobilized to form modified particles for crosslinking a (car-boxylated) diene latex.
    The advantage here is that the particles do not or only very slowly migrate from the prophylactic article. By slow is meant that the migration time is much greater than the application time of the prophylactic article. It is thus prevented that the crosslinking agent comes into contact with the human skin, whereby the allergy potential of the prophylactic article can be significantly reduced. Even during the storage of the prophylactic articles, the migration of the crosslinking agent from the prophylactic article can be prevented or significantly reduced. In addition, leaching processes for removing unbound process chemicals can be shortened or even saved. The immobilized crosslinker may be a multifunctional monomer and / or polymer or mixtures thereof. With the method, a prophylactic article can be produced which has very good mechanical properties and a high resistance to aging and gamming. Also, an influence on the film formation during the manufacturing process, in particular the dipping process, could not be proven, so that no further measures are necessary for this. A further advantage of the process is the fact that precrosslinking of the (carboxylated) diene latex is not required, so that continuous mixing processes can be used and processes can be accelerated. The method makes possible an energy-efficient, sustainable and production-efficient production of hypoallergenic prophylactic articles, in particular surgical and examination gloves.
    According to a preferred embodiment of the method it can be provided that only the modified particles are used as crosslinking agent. It can thus be further improved the above-mentioned effects, wherein additionally can be achieved by the omission of heavy metal ions such as Zn2 + from ZnO, the allergy potential can be further reduced (zinc can, for example, with carboxylic acids such as acetic acid from the Elastomer extracted). In addition, no interference with another crosslinking system can take place, as partially reported in the prior art.
    According to a further preferred embodiment of the method can be provided that are used as inorganic particles silicate-based particles. With silicate-based particles, in addition to the covalent crosslinking of the molecules of the (carboxy-lated) diene latex, ionic crosslinking can additionally be achieved via their cation, for example Ca 2+. It is thus easier to dispense with additional crosslinking agents, for example the frequently used ZnO, in order to achieve higher tear strengths of the prophylactic article. Higher tear strengths are achieved via the ionic network sites, while covalent bonds bring about an improvement with regard to the reduction of the hole-formation susceptibility of the prophylactic article when worn. After the particles are embedded, in particular, physically and / or mechanically bound in the elastomer, they also do not migrate out of the prophylactic article, so that no problems arise with powders with regard to the allergy potential of the prophylactic article.
    According to another embodiment of the method it is provided that the silicate-based particles are selected from a group consisting of silicates with polyvalent cations, zeolites, S1O2 and mixtures thereof. It is thus achievable a further improvement of the above-mentioned effects. In addition, with zeolite, a better incorporation of the silicate-based particles into the elastomer layer can be achieved over its cavities, so that the silicate-based particles can be more easily connected physically or mechanically to the first layer. In addition, the added benefit can thus be achieved that these particles can also have an adsorbing effect on any pollutants that migrate into the first layer from the outside or from the inside of the prophylactic article.
    According to an embodiment variant it can be provided that the zeolite is a natural zeolite. In addition to the cost factor - synthetic zeolites are significantly more expensive than natural - it is advantageous that natural zeolites have a more heterogeneous structure compared to synthetic ones. Thus, the mechanical properties of the prophylactic article are in general less influenced by the natural zeolite than by the use of a synthetic zeolite.
    In the course of tests carried out, a zeolite which has been selected from a group consisting of clinoptilo-lith, chabazite, phillipsite, analcime and mixtures thereof has proven particularly suitable. This is all the more surprising as these zeolites belong to different structural classes.
    It is also advantageous if the particles are modified with an excess of crosslinking agent, in particular with siloxanes having epoxy groups, to form a multilayer structure of the crosslinking agent on the particles. By covalent attachment of the crosslinking agent to the particles, a portion of the anchor groups / network-forming groups is hydrolyzed. These are therefore no longer available for networking. For this reason, the use of an excess of crosslinking agent is advantageous because it forms a multi-layered structure on the surface of the particles. In this multi-layer structure, the first layer is still covalently bound to the particles and hydrolyzed, but in the other layers there is no hydrolysis of the anchor groups / network-forming groups, so that overall the reactivity of the particles provided with the crosslinking agent is better.
    The crosslinking of the (carboxylated) diene latex molecules can be carried out thermally. Thus, the crosslinking of the latex molecules can already take place during the drying of the latex film which has appeared on the dip mold, as a result of which an increase in the efficiency of the process can be achieved. In particular, the variant embodiment is advantageous if the particles are mixed with an excess of crosslinking agent.
    Preferably, the pH of the (carboxylated) diene latex is adjusted to a value of greater than or equal to 9. With pH values 9 and above, a clear improvement in the reaction kinetics was observed, as a result of which the crosslinking of the molecules can take place more rapidly.
    The crosslinking agent can be selected from a group consisting of polyfunctional epoxies, polyfunctional silanes, polyfunctional siloxanes, polyfunctional thiols. It is advantageous if these are (i) water-soluble, since no emulsifier is required when introducing the crosslinking agent into the latex mixture; (ii) have more than one epoxide function for crosslinking the rubber chains. Preferably, the multifunctional epoxies have a structure such that the hydrolysis product has "nourishing" properties, such as diglycidyl terminated polyethyleneglycol derivative, epoxy sorbitol derivative, derivative of a sugar alcohol. Furthermore, for example. Mono- and polysaccharides can be used with epoxy functionalities.
    An advantage of the polyfunctional thiols is when they (i) have a high molecular weight (molecular weight between 200 g / mol and 4000 g / mol); (ii) have a high mercapto-equivalent number (at least 20%, especially at least 50%, of the monomer units should bear SH groups); (iii) are accessible via simple synthetic strategies.
    An advantage of the polyfunctional silanes and siloxanes is that they (i) carry more than one reactive group (e.g., CoatOSil MP200 results in higher tear strengths than 3-glycidoxypropyltrimethoxysilane); (ii) the silanes carry at least one trialkoxy group (for coupling to the filler and for formation of oligolayers via physical interactions).
    In addition to the exclusive use of the modified particles as crosslinkers, according to another embodiment it can be provided that an additional crosslinking agent is a polyfunctional monomer and / or polymer which is added to the (carboxylated) diene latex and dissolved therein. The polyfunctional monomers and / or polymers have the advantage of ease of handling because the soluble monomer and / or polymer can be blended without prior dispersion or emulsion in the latex. This additional additional covalent crosslinking sites can be formed in the elastomer. In addition, the modulus of the prophylactic article can thus also be better adjusted, in particular if, according to a further embodiment, an organic monomer and / or polymer having a molecular weight between 170 g / mol and 4000 g / mol is used. It can thus be achieved a better comfort for the user of the prophylactic article. This is important insofar as a change in the mechanical properties of the prophylactic article was observed by the incorporation of the particles in the elastomer layer.
    For a better understanding of the invention, this will be explained in more detail with reference to the following figures.
    Show it:
    1 shows the degree of swelling of crosslinked XNBR latex films (not pre-crosslinked, thermal crosslinking in the course of drying at 100 ° C. for 15 min) at different Rima Sil 1200 concentrations;
    FIG. 2 depicts the covalent (left) and ionic (right) crosslinking of XNBR; FIG.
    Fig. 3 Tear strengths of crosslinked XNBR latex films at different Rima Sil 1200 concentrations (no pre-crosslinking, thermal crosslinking in the course of drying at 100 ° C for 15 min);
    Fig. 4 tensile strengths of XNBR latex films at different Prävulkanisationszeiten and when using 5phr Rima Sil 1200;
    Fig. 5 shows elongations at break of crosslinked XNBR latex films at different Rima Sil 1200 concentrations (no pre-crosslinking, thermal crosslinking during drying at 100 ° C for 15 min);
    Fig. 6 Stress at 50% elongation of crosslinked XNBR latex films at different Rima Sil 1200 concentrations (no pre-crosslinking, thermal crosslinking in the course of drying at 100 ° C for 15 min);
    Fig. 7 Tear strengths of XNBR latex films at different particle types and particle concentrations;
    Fig. 8 shows elongations at break of XNBR latex films at different particle types and particle concentrations;
    Fig. 9 Stress values at 50% elongation of XNBR latex films at different particle types and particle concentrations;
    Fig. 10 Tear strengths of XNBR latex films at different particle types and particle concentrations (crosslinker concentration: 5phr). All standards cited in the specification refer to the version valid at the time of filing the application, unless otherwise stated.
    The invention relates to a method for Flerstellen a prophylactic article.
    The prophylactic article is preferably a flat shoe, in particular a surgical flat shoe (surgical glove) or an examination glove. However, the prophylactic article can also be, for example, a fingerstall, a catheter, a condom, a (medical) balloon, a nipple, etc. In general, the prophylactic article is preferably a dipping article, ie a product which is produced by means of a dipping process.
    In the following, only the training of the prophylactic article as a glove will be discussed. However, the statements on this can also be applied to other elastomeric articles, in particular dipping articles which are produced by a dipping process.
    The glove comprises or consists of a diene elastomer (diene rubber), in particular a carboxylated diene elastomer.
    The elastomer of the elastomeric layer can be based on both a natural and a synthetic latex. These may be selected from a group consisting of or consisting of natural rubber (NR), polyisoprene latex (IR), nitrile butadiene rubber latex (NBR), carboxylated nitrile butadiene rubber latex (XNBR), carboxylated butadiene latex (XBR), chloroprene latex (CR), styrene-butadiene latex (SBR), carboxylated latexes made from polymer blends, and mixtures thereof.
    In particular, a carboxylated nitrile-butadiene rubber latex is used to make the elastomeric layer. This preferably has a proportion of acrylonitrile between 15 wt .-% and 40 wt .-%, in particular between 20 wt .-% and 35 wt .-%, on.
    The prophylactic article or the elastomeric glove is preferably produced by a dipping process. Such dipping methods are known in principle from the prior art, so that reference is made to the relevant state of the art for details.
    Essentially, in this method, a dip mold (usually several dipping dies are used in serial production) is immersed in a dipping bath. The dip mold has the shape of the finished product, that is, for example, the shape of a hand.
    In the immersion bath, the respective elastomer latex is presented, which is to be dipped onto the dip mold.
    In principle, however, any other suitable form may also be used in the processes described in this description, in particular if the elastomer layer is not produced by a dipping process. The elastomer layer can also be produced, for example, by brushing or spraying the elastomer latex onto a mold. Likewise, other suitable methods of applying the latex to a mold are applicable.
    The term elastomer latex is used in this description according to the usual use in the jargon. Accordingly, an elastomer latex is a dispersion of uncrosslinked or precrosslinked or crosslinkable polymer molecules to produce an elastomer. Pre-crosslinked elastomer latices can therefore also be processed within the scope of the invention, it being possible for the precrosslinking to take place in particular by means of the crosslinking agents mentioned in this description.
    However, it is also possible that the elastomer latex is crosslinked only after application to the mold, that is, the applied elastomer latex.
    A common process route of a coagulation dipping process may comprise, for example, the following process steps: washing the dipping form and degreasing with an organic solvent; - preheating the dipping form; - Immerse the dipping form in a first dip with a coagulant; - drying of the first layer that has appeared; dipping the immersion mold in another immersion bath to form the elastomer layer; - dry / vulcanize (crosslink); - remove the dive article from the mold. In the event that the elastomeric glove is made multi-layered, additional layers of the first elastomeric latex or of another elastomeric latex or other polymer may be surfaced or generally applied. For example, a polymer layer can be emerged as the last layer, which after removal of the flat shoe from the dipping form passes through the resulting turning of the flat shoe to the inside of the flat shoe. Such polymer layers may, for example, be designed as sliding layers in order to improve the attractability of the elastomeric glove.
    The elastomeric glove can thus be formed on one or more layers, wherein the individual layers may consist of mutually different materials or of the same materials. It is also possible that two or more layers of the elastomeric glove are made of the same material and one or more layers of a different material.
    Since all this is known, it should not be discussed further.
    In this context, "materials" are understood to be elastomers and polymers, but the elastomeric glove has at least one layer of an elastomer.
    The terms vulcanization and crosslinking are used synonymously in this description.
    For crosslinking the (carboxylated) diene elastomer latex, this, i. E. in particular, the dipping bath for Fierstellung the at least one layer of the (carboxylated) diene elastomer, a crosslinking agent added. In addition, the diene elastomer latex or the dipping bath may comprise at least one further additive, such as at least one emulsifier, at least one anti-aging agent, at least one dye, at least one antiozonate, as known per se for the preparation of dipping articles. The total amount of these additives may be between 0.1 phr and 10 phr, based on the total composition of the diene elastomer latex or of the dipping bath.
    The crosslinker is added to the (carboxylated) diene elastomer latex immobilized on inorganic and / or organic particles to form modified particles. The particles are not soluble in the (carboxylated) diene elastomer latex. In addition, another monomeric and / or polymeric based crosslinking agent may be dissolved or emulsified in the (carboxylated) diene elastomer latex (for example, thiols or non-polar epoxides). In this case, a multi-functional monomer and / or polymer is used as another crosslinking agent. However, it is also possible that the particles are modified with the multifunctional monomer and / or polymer serving as a crosslinking agent.
    In the preferred embodiment of the process, no further crosslinking agents are used, i. in that only the modified particles are used as crosslinking agent.
    It is further preferred if the (carboxylated) diene elastomer latex is crosslinked after application to the mold. However, pre-crosslinking of the (carboxylated) diene elastomer latex is also possible, for example also with the particles on which the crosslinking agent is immobilized.
    The particles used may be inorganic and / or organic in nature.
    The organic particles may be selected from a group consisting of or consisting of polydimethylsiloxanes, silicone resins, urea resins, epoxy resins, diene elastomers.
    The inorganic particles may be selected from a group consisting of or comprising silicate-based particles, S1O2, carbonates, oxides.
    Preferably, silicate-based particles are used as the inorganic particles.
    The silicate-based particles are preferably selected from a group comprising or consisting of silicates with polyvalent cations, for example wollastonite, zeolites, and mixtures thereof.
    According to a variant embodiment of the elastomeric glove and its method of preparation, the silicate-based particles consist of a zeolite, in particular a natural zeolite, it being preferred to use zeolite Klinop-tilolite, chabazite, phillipsite, analcime and mixtures thereof. According to a further preferred embodiment, a clinoptilolite is used as the natural zeolite. However, it is also possible that the zeolite is a synthetic zeolite.
    Depending on the deposit, natural zeolite has a greater or lesser amount of accompanying minerals, in particular quartz. For the use of natural zeolite in the process of making the elastomeric glove, use is preferably made of a natural zeolite having a degree of purity of at least 85%, especially at least 90%, i. at least 80% or 90% of the silicate-based particles consist of the zeolite.
    The particles are added to the (carboxylated) diene elastomer latex. As a result, these particles are incorporated or embedded in the layer of the elastomer latex, so that the particles are thus incorporated physically and / or mechanically. Near-surface particles (with respect to the (carboxylated) diene elastomer layer) may protrude beyond the elastomeric layer, in which case at least 90%; especially 100%, these particles are also coated with the elastomer of the elastomer layer. It is thus possible to produce a surface roughness which can improve the grip of the glove or which can improve the bond strength of the elastomer layer with a further layer, by additionally achieving mechanical anchoring of the particles in the further layer.
    The protrusion of the particles over the surface of the elastomer layer can be achieved or adjusted by the particle size of the particles and / or the layer thickness of the elastomer layer.
    The particles may have a particle size corresponding to a particle size distribution with a mean particle diameter (dso) of 0.5 μm to 7.5 μm in a top cut (d9s) of 2 μm to 20 μm.
    The sizes of the natural zeolite particles were determined with a Malvern Mastersi-zer, Hydro 2000G (wet cell). The particle size of the synthetic zeolites and the silicate particles were taken from the manufacturer's data sheet.
    Used particles for the following examples:
    Zeolite 1: natural zeolite; dio = 2 μιτι; dso = 5 μιτι; d98 = 15 μιτι (BET: 33.2 m2 / g).
    Zeolite 2: natural zeolite; dio = 1.7 μιτι; dso = 3 μιτι; d98 = 8.5 μιτι.
    Zeolite 3: natural zeolite; dio = 0.3 μιτι; dso = 1.4 μιτι; d98 = 5.5 μιτι.
    Zeolite 4: synthetic zeolite; rod-shaped: 300x700nm (BET: 300 m2 / g).
    Silica 1: Amorphous silica (Sigma-Aldrich): 0.2-0.3 pm (aggregates) (BET: 200 m 2 / g).
    Silica 2: silicic acid designated KS 400 by Grace, BET = 180 m2 / g.
    Rima Sil 1200: Ca silicate (CaSiOs), d5o = 2pm.
    The layer thickness of the elastomer layer can be between 30 μιτι and 500 μιτι.
    In principle, the particles can have any habit. Preferably, however, particles are used which are at least approximately round or rounded, ie have no sharp breaklines.
    The particles are preferably contained in the elastomer layer in a proportion by mass of 1 phr (parts per hundred rubber) to 20 phr, in particular from 3 phr to 10 phr.
    According to another embodiment, the particles may preferably have a BET specific surface area of between 1 g / m 2 and 300 g / m 2. It can thus improve the mechanical properties due to the interactions of the particles with the elastomer matrix. In addition, more covalent bonds can be formed on the surface of the particles.
    Crosslinking agents selected from the group consisting of or comprising (polyfunctional) epoxies, (polyfunctional) silanes, dialkoxysilanes, trialkoxysilanes, trichlorosilanes can be used to modify the particles. Examples of these are (3-glycidoxypropyl) trimethoxysilane, polyglycidoxypropyltrimethoxysilane, (3-glycidoxypropyl) triethoxysilane, (3-glycidoxypropyl) trichlorosilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 5, 6-epoxyhxyltriethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) methyldimethoxysilane.
    The particles are usually superficially modified. However, when using particles having voids, such as zeolites, the modification may include the surface of the voids.
    The particles are preferably modified with an excess of crosslinking agent to form a multi-layered structure of the crosslinking agent on the particles. However, it is also possible to use a lower amount of crosslinking agent so that the crosslinking agent is in deficit to the surface to be modified, i. the reactive groups to be modified on the surface of the particles, is present.
    The modification of the particles can be carried out as follows. However, it is also possible to use already modified particles. Such particles are available, for example, Grolman (Rima Sil 1200 based on Ca silicate), EM Hoffmann Minerals (Aktisil EM), quartz movements (Tremin 283-400EST).
    As already stated above, in addition to the modified particles, a further crosslinking agent can also be used in the form of (polycarboxylic) n-elastomer latex-soluble or dispersible or emulsifiable polyfunctional monomers and / or polyfunctional polymers. The term "polymer" in the sense of this description generally includes molecules starting from two monomer units, that is, molecules starting from dimers. The polyfunctional monomers and / or polymers are preferably selected from a group comprising or consisting of polyfunctional in) epoxides, polyfunctional silanes, polyfunctional siloxanes, polyfunctional thiols , as well as mixtures thereof.
    Examples of these are short-chain: sorbitol polyglycidyl ether, glycerol glycidyl ether, 1,6-hexanediol diglycidyl ether, resorcinol diglycidyl ether, 1,4-cyclohexanedimethanol diglycidyl ether, diglycidyl 1,2-cyclohexanedicarboxylate, ethylene glycol diglycidyl ether long-chain: diepoxy-terminated polyethylene glycol, diepoxy-terminated Polypropylene glycol, polyglycidyl methacrylate (homopolymers and copolymers with ethylene glycol units, ethylene units, etc.), polyglycerol polyglycidyl ether.
    Short-chain compounds are monomeric, high molecular weight, polyfunctional compounds, in particular those compounds having a molecular weight of at least 170 g / mol. Long-chain compounds have at least two or more repeat units (dimers and larger).
    In general, the term "polymer" in the context of the invention also includes oligomers.
    In general, the term "high molecular weight monomer" describes a monomer having a molecular weight of preferably at least 170 g / mol, in particular between 170 g / mol and 4000 g / mol.
    It is also advantageous if the pH of the (carboxylated) diene elastomer latex is adjusted to a value of greater than or equal to 9. For this purpose, for example, an aqueous KOH solution (1 wt .-% to 5 wt .-%) can be used. In general, suitable basic substances, such as alkalis, can be used for this purpose.
    In the preferred embodiment of the process, the crosslinking of the (carboxylated) diene elastomer molecules takes place thermally, in particular during the drying of the (dipped) layer of the (carboxylated) n-elastomer latex. The temperature can be between 90 ° C and 140 ° C. The crosslinking can take place for a period of between 5 minutes and 20 minutes.
    A crosslinking agent can be used which has a molecular weight between 170 g / mol and 4000 g / mol, in particular between 170 g / mol and 1700 g / mol (polymeric, water-soluble compounds in accordance with DIN 55672-3: 2007-08 (GPC)). or over the viscosity of liquid polymers according to DIN 51 562-1). For example, ethylene glycol diglycidyl ether (molecular weight 170 g / mol) or diethylene glycol diglycidyl ether (molecular weight 218 g / mol) can be used. It is thus also possible to set the (50%) modulus of the elastomer glove to a desired value. The modulus of the elastomeric glove can be adjusted over the chain length of the crosslinking agent.
    The method can produce a prophylactic article, particularly a glove, comprising a layer of a (carboxylated) n-type elastomer wherein the (carboxylated) diene elastomeric chain of the (carboxylated) diene elastomer is covalently crosslinked via organic molecules and optionally ionically via metal cations, the Metal cations are in particular part of inorganic particles, and wherein the organic molecules are immobilized on the inorganic particles.
    The elastomer gloves produced by the process have a good skin compatibility. On the basis of conducted investigations no skin irritation and no sensitization potential could be determined.
    In the course of the testing of the networking process, i.a. following experiments were performed. These are only selected examples, as the reproduction of all experiments would go beyond the scope of this description.
    Table 1 below summarizes the materials used in the experiments on the use of modified particles (fillers).
    Table 1: Materials used for crosslinking with modified particles
    The epoxy-functionalized particles were predispersed in different concentrations (3 to 7.5 phr) in deionized water with an Ultraturrax (10 min at room temperature) and then added to the latex mixture (pH = 10, ~ 25 drc. (Dry rubber content)) ,
    Generally, the (carboxylated) diene elastomer latex may have a solids content of (carboxylated) diene elastomer between 10 drc (dry rubber content) and 60 drc.
    The mixture was added with an anti-aging agent (0.5 phr Ralox) and stirred for about 15 minutes at room temperature. Subsequently, the films were prepared by the above-mentioned coagulation dip method. The latex mixture was slightly stirred during the dipping process with the aid of a magnetic stirrer in order to prevent sedimentation of the particles.
    The agitation of the latex mixture is preferably used generally in the process.
    The films were dried at 100 ° C for 15 min. No pre-crosslinking or latex ripening was needed because the crosslinking occurred during drying of the films at 100 ° C.
    Subsequent reaction is based on thermal crosslinking with epoxy-functional inorganic particles as crosslinking agent. Preference is given in advance to the adjustment of the pFI value of the latex mixture with 1 wt .-% KOFI to pH = 10 to 10.5, since the reaction is catalyzed at higher pFI values.
    Successful crosslinking of XNBR latex using inorganic functional particles as non-extractable crosslinking agents was first performed by equilibrium swelling in chloroform (determined by: (1) Macromolecules 2008, 41, 4717-4729, (2) J. Appl. Polym. 129 (5), 2735-2743 and (3) Zaborski, M .; Kosmalska, A., Gulinski, J. Kautsch, Gummi Kunstst. 2005, 58, 354). The results are shown in Fig. 1 (abscissa: concentration of crosslinking agent in phr; ordinate: swelling degree) and show that the degree of crosslinking correlates with the concentration of crosslinking agent and higher crosslinking concentrations result in higher crosslinking densities.
    It is therefore preferable to use a concentration of crosslinking agent between 1 phr and 15 phr, in particular between 1 phr and 7.5 phr.
    In addition to the low extractability, the advantage of the epoxy-functional particles based on Ca silicates that can be formed with a crosslinking agent covalent and ionic crosslinking sites, as shown in Fig. 2 (left covalent bonds, right ionic bonds). Through this combined approach it is also possible to produce heavy metal free (ZnO free) Flandschuhe.
    Fig. 3 shows the tensile strength (ordinate in MPa) as a function of the amount of particles used. On the abscissa, the bars are shown in groups of three for 3 phr, 5 phr and 7.5 phr particles from left to right for non-sterile and non-aged, non-sterile and aged, sterile and non-aged as well as sterile and aged samples.
    Generally, sterilization can be by gamma radiation with a Co-60 source and a radiation dose of 25kGy. Aging can generally be done by hot air aging at 70 ° C in a convection oven over 7 days.
    As can be seen in Figure 3, the best tear strengths were achieved with 3 phr particles, with the crosslinked XNBR latex films being characterized by good aging and gamma resistance.
    Subsequently, the influence of a prevulcanization on the mechanical properties was investigated. In FIG. 4, the corresponding values are shown for this purpose. The particle content was 5 phr each. Tensile strengths (as determined by ASTM Standard D412-98a, "Standard Test Methods for Vulcanized Rubber and Thermoplastic Elastomers Tension", Annu. Book ASTM Stand. 09.01 (2002)) are plotted on the ordinate in MPa. The bars within a group of four are from left to right for non-sterile and non-aged, non-sterile and aged, sterile and non-aged as well as sterile and aged samples. The abscissa indicates the pre-crosslink times in minutes.
    Analogous to crosslinking with water-soluble polymeric Epoxidvernetzungsmitteln no improvement of the mechanical properties by a thermal pre-crosslinking (1 -3h at temperatures in the range of 50-60 ° C) is observed.
    FIG. 5 shows the results of the strain measurements and FIG. 6 shows the results of the module measurements. The corresponding values can be read on the ordinate. The abscissa distribution corresponds to that of FIG. 3.
    At crosslinker concentrations in the range of 3 to 5 phr, the elongations at break consistently exceed 700% and the corresponding stress values at 50% elongation are in the range of 1.2 to 1.6 MPa.
    Attempts have also been made to incorporate the silane component of surface functionalization directly and without particles into the latex mixture. Only lower degrees of crosslinking or worse mechanical properties could be measured. This was demonstrated by experiments with CoatOSil MP200, which has been applied as an organic shell to the Rima Sil particles. The results of the tensile test show that the tensile strengths are below 20 MPa regardless of the silane concentration. A thermal pre-crosslinking of the latex mixtures at 60 ° C leads to an additional reduction of the strengths below 10 MPa.
    This may be due to condensation of the silanes into oligosilicic acids and indicates that the particles have a particular function for high mechanical strengths of the elastomeric film.
    To demonstrate the applicability of this process to other types of fillers, zeolites have been modified with functional silanes. Extensive investigations have shown that the functionalization of zeolites and silicas is possible by the condensation reaction with trialkoxysilanes. Modification levels of up to 5% by weight for zeolites and 6% by weight for silicate particles (based on the inorganic support) were realized (detected by means of thermogravimetry). Here, too, it could be observed that the epoxy groups are at least partially hydrolyzed during the modification and thus the reduced reactivity occurs (this was shown by spectroscopic methods and correlation with the corresponding mechanical properties). For this reason, it is advantageous, as described above, to use coated particles, i. Particles in which the first layer is chemically bound to the particle surface and hydrolyzed, but formed in silane excess, a multilayer system having unhydrolyzed anchor groups. The above-described improved crosslinking with Rima Sil 1200 particles is also based on this principle, since the Ca silicates have been functionalized with a significant excess of silane and the organosilane shell can already be seen as a coating.
    Based on these studies, zeolites and silicas have been modified with an excess of silane and used as crosslinking agents for thermal crosslinking of XNBR latex. For modification, zeolite suspensions (zeolites 1 to 4) in ethanol were prepared in the first step at a concentration of 100% (w / v) and then 50% (w / v) 3-glycidoxypropyltrimethoxysilane or 50% (w / v) CoatOSil MP200 added. The suspensions are mixed for one hour at room temperature with a magnetic stirrer and then dried the particles for 2 h at 120 ° C (remove the solvent). The results are shown in FIGS. 7 to 8.
    In these figures, Ca silicates modified in each case with CoatOSil (on the left next to the vertical line) are compared with the correspondingly modified zeolites (on the right next to the vertical line). In Fig. 7, the ordinate is the tensile strength in MPa, in Fig. 8, the elongation in MPa and in Fig. 9, the modulus at 50% elongation applied. On the abscissa, the proportions of particles in the latex are plotted in phr.
    In the course of the work, the influence of the particle size on the mechanical properties was also investigated. In the case of the coated zeolite particles used, no significant influence of the particle size could be observed. The tear strengths of crosslinked XNBR latex films with the addition of 10 phr zeolite particles modified with CoatOSil MP200 (no pre-crosslinking, thermal crosslinking during drying at 100 ° C for 15 min) were consistently between 22 MPa and 25 MPa.
    With amorphous silicas and Ca silicates (Rima Sil) higher mechanical strengths can be achieved at lower crosslinker concentrations (5phr). The tear strengths of cross-linked XNBR latex films with the addition of 5phr particles modified with CoatOSil MP200 (no precrosslinking;
    Crosslinking in the course of drying at 100 ° C for 15 min) were about 30% higher than those of the investigated zeolites, from which the influence of the particulate material can be concluded.
    Analogously to the modification of zeolites, silica particles (silicate 1, silicate 2, silica KS 400 from Grace) were coated by means of CoatOSil MP200 according to the above modification protocol. The mechanical properties of their corresponding XNBR latex films (no pre-crosslinking, thermal crosslinking during drying at 100 ° C.) are comparable to the results of Rima Sil particles. At 5phr slightly lower tear strengths can be observed when using the modified zeolite particles (Figure 10, ordinate: ultimate tensile strength in MPa, abscissa from left to right: Rima Sil, zeolite, silica), which is highly likely to affect the porous filler structure (and the resulting linked extended migration pathways of the non-covalently bound epoxy crosslinking agent).
    In another experiment, the thermal crosslinking of XNBR latex with commercially available epoxy-functional silica was performed by Hoffmann Minerals. The degree of modification of these particles (Aktisil EM) is significantly lower than that of the Rima Sil 1200 particles, while the particle sizes are in a similar range, as shown in Table 2 below.
    Table 2:
    The mechanical strengths of the crosslinked XNBR latex films are in the range of the uncrosslinked reference (uncrosslinked dipped and dried XNBR latex film without addition of any crosslinking chemicals and fillers, pFI value of 10 of the latex blend was discontinued) and suggest inadequate crosslinking. The results confirm the influence of the degree of modification of the functionalized particles on the crosslink density and, associated therewith, the mechanical properties of the crosslinked XNBR latex films. It has been found that a degree of modification of the particles, measured by means of thermogravimetric analysis (TGA) of at least 2%, in particular between 4% and 60%, is advantageous.
    The test results for carrying out the process with polyfunctional monomers and / or polymers as further crosslinking agents are reproduced below. Table 3 summarizes the educts used for this purpose.
    Table 3: materials used for crosslinking with monomers and / or polymers
    Preparation of latex blends, dipping and cross-linking
    The water-soluble crosslinking agent was added at various concentrations (0.5 to 7.5 phr) of the latex mixture (pH = 10, ~ 25 drc.) Containing modified particles as described above. The mixture was then mixed with an anti-aging agent (2 phr Ralox) and stirred for about 15 minutes at room temperature. Subsequently, the films were prepared by the above-described coagulation dip method, and the films were dried at 100 ° C for 15 minutes. No pre-crosslinking or latex maturation was needed. The crosslinking took place during the drying of the films at 100 ° C.
    Subsequent reactions are based on the thermal crosslinking with monomeric and / or polymeric Epoxidvernetzern. It is advantageous in advance to adjust the pH of the latex mixture, for example with 1 wt .-% KOH to pH = 10, since the reaction is catalyzed at higher pH values.
    Reaction of a carboxylated elastomer with an epoxide
    Acid and base catalyzed ring opening of epoxides.
    The successful cross-linking of XNBR latex with the addition of selected water-soluble polymeric cross-linking agents was demonstrated by equilibrium swelling in chloroform (see above for measurement basis).
    The crosslink density increases with increasing crosslinking time and crosslinker concentration, whereby the reactivity of the crosslinkers of DEPEG-500 <SPE <GE100 increases.
    In addition to equilibrium swelling, crosslinking of XNBR latex was also detected by tensile testing with the addition of selected water-soluble monomeric and polymeric crosslinking agents.
    When using DEPEG-500, mechanical strengths in the range of 22 ± 2 MPa can be observed from a concentration of 5phr. At lower concentrations (0.5 to 3 phr) a low crosslink density is achieved and tear strengths are below 10 MPa. Increasing the crosslinker concentration to 7.5 phr results in a further increase in strengths of up to 35 ± 2 MPa. Therefore, a concentration of 5 phr to 7.5 phr is preferred.
    Very good mechanical strengths and aging and gamma resistances were also observed with DEPEG-200 in a concentration range between 3 phr and 7.5 phr ((non-sterile / non-aged: 26 MPa-40 MPa, non-sterile / aged: 37 MPa -26 MPa, sterile / non-aged: 28 MPa -24 MPa, sterile / aged: 25 MPa -35 MPa).
    Since similar results have been obtained with other multifunctional monomeric and polymeric crosslinking agents, a concentration of 1 phr to 7.5 phr of multifunctional monomeric and / or polymeric crosslinking agents in the latex is generally preferred.
    Further, excellent hard air aging (7 days storage at 70 ° C) and gamma resistance (25 kGy) are observed.
    In addition, the stress at 50% elongation is also in the range of 1.2 to 1.4 MPa, even at high tensile strengths, and is hardly increased even after use of 5 phr of crosslinking agent even after hot air aging and gamma sterilization. This is particularly advantageous for the production of surgical gloves, since a low tension at 50% elongation is a criterion for a comfortable fit.
    Analogous to the crosslinking with DEPEG-500, very good mechanical properties (even after gamma sterilization) were also detected at higher concentrations (7.5 phr) when using SPE (epoxy sorbitol). At a concentration of 5 phr SPE, mechanical property values were measured between 12 MPa and 32 MPa (non-sterile / non-aged: 30 MPa-32 MPa, non-sterile / aged: 12 MPa -14 MPa, sterile / non-aged: 30 MPa -32MPa; sterile / aged: 13 MPa -15 MPa). However, a disadvantage is a lower resistance to aging of the crosslinked XNBR latex films. After storage at 70 ° C for 7 days, the strengths drop from 30 ± 2 MPa to less than 15 MPa.
    In addition, when SPE is used as the water-soluble high molecular weight crosslinking agent, a marked increase in stress at 50% elongation is observed, which is detrimental to the wearing comfort of the elastomeric glove. At 7.5 phr SPE, values in the range of 1.6 to 1.8 MPa are obtained.
    When GE100 is used as a crosslinking agent, even at low concentrations (1 and 3 phr) very good mechanical strengths are achieved, which are in the range of 20 to 27 MPa. With higher crosslinker concentrations (7.5 phr), a further increase in tear strengths is observed (37 ± 2 MPa). At a concentration of 5 phr, values between 22 MPa and 40 MPa are obtained (non-sterile / non-aged: 35 MPa-40 MPa; non-sterile / aged: 32 MPa-35 MPa; sterile / non-aged: 36 MPa -38 MPa sterile / aged: 22 MPa -23MPa). The crosslinked XNBR latex films are characterized by a very good gamma resistance. A disadvantage is the lower resistance to aging, which leads to a reduction in tear strength, especially at lower crosslinking agent concentrations.
    In summary, it can be concluded from the results that high tear strengths (30 ± 2 MPa) and gamma resistances (after gamma sterilization: 30 ± 2 MPa) have been achieved with all three investigated crosslinking agents. In terms of resistance to hot air aging or low modulus at 50% elongation, DEPEG-500 has clear advantages over GE-100 and SPE.
    Based on these results, the module value of the crosslinked XNBR latex films was adjusted in a targeted manner by the molecular weight of the epoxide-terminated polyethylene glycol derivative (DEPEG). On the one hand, with a lower molecular weight, a very high strength (up to 40 MPa) is achieved while the modulus increases. This is particularly interesting for the production of examination gloves, where high strengths are in the foreground and the module (due to the layer thickness) plays only a minor role. Although XNBR films crosslinked with DEPEG-500 (average molecular weight) give somewhat lower strengths, modulus values are significantly lower. This variant is more suitable for the production of surgical gloves, where the main focus is on a low module.
    However, if the molecular weight of the crosslinking agent is in the range of 1,000 g / mol, the 50% modulus can be brought below 1 MPa, but the corresponding tear strengths are also below 15 MPa. The results therefore show that over the chain length of the crosslinking agent, a balance between tear strength and modulus can be set. Therefore, the above-mentioned chain lengths of the polymeric crosslinking agents are preferred.
    In further investigations, PolyLac 582N was crosslinked with 5 phr DEPEG-200 as another alternative latex type at different pH values. The results clearly show that successful crosslinking of PolyLac 582N succeeds
    Further crosslinking was carried out with a mixture consisting of epoxide-modified particles and high molecular weight Epoxidvernetzern. For this purpose, epoxy-functionalized particles (RimaSil 1200) were predispersed in different concentrations (1.5 phr to 5 phr) in deionized water with an ULTRA-TURRAX (10 minutes at room temperature) and then the latex mixture (pH = 10.2; 25 drc.) Was added. Subsequently, a water-soluble high molecular weight, multiply functional epoxide (diepoxy-terminated polyethylene glycol, DEPEG-200) was added in different concentrations (1.5 to 5 phr) and the mixture with an anti-aging agent (2 phr ionol LC). The mixtures were stirred for about 15 minutes at room temperature. Subsequently, the films were prepared by coagulation dipping method (see above), wherein the latex mixture during the dipping process was easily stirred with the aid of a magnetic stirrer to prevent sedimentation of the particles. The films are dried at 100 ° C for 15 minutes. No pre-crosslinking or latex ripening was needed because the crosslinking occurred during drying of the films at 100 ° C. Another advantage is the adjustment of the pH of the latex mixture with 1 wt .-% KOH to pH = 10.2, since the reaction is catalyzed at higher pH.
    Of the XNBR latex films produced (non-sterile, non-aged), the tear strengths were about 31 MPa for 1.5 phr DEPEG-200 and 1.5 phr Rima Sil 1200, about 28 MPa for 2.5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, about 33.5 MPa for 5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, about 25 MPa for 3.75 phr DEPEG-200 and 3.75 phr Rima Sil 1200 and about 30 MPa for 2.5 phr DEPEG-200 and 5 phr Rima Sil 1200.
    The results of the tensile test show that even crosslinking agent mixtures consisting of a functional filler and a high molecular weight, multiply functional epoxide lead to very good mechanical strengths. Especially at low crosslinker concentrations, the combination of the selected crosslinkers results in high tear strengths.
    The modulus at 50% elongation of these latex films was about 1.35 MPa for 1.5 phr DEPEG-200 and 1.5 phr Rima Sil 1200, about 1.45 MPa for 2.5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, approx. 1.4 MPa for 5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, approx. 1.35 MPa for 3.75 phr DEPEG-200 and 3.75 phr Rima Sil 1200 and approx 1.6 MPa for 2.5 phr DEPEG-200 and 5 phr Rima Sil 1200.
    The elongation of these latex films was about 700% for 1.5 phr DEPEG-200 and 1.5 phr Rima Sil 1200, about 650% for 2.5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, about 660 % for 5 phr DEPEG-200 and 2.5 phr Rima Sil 1200, about 620% for 3.75 phr DEPEG-200 and 3.75 phr Rima Sil 1200 and about 620% for 2.5 phr DEPEG-200 and 5 phr Rima Sil 1200.
    In further experiments, the separate addition of trialkoxysilane and zeolite (unmodified) was investigated. To this end, 5 phr unmodified zeolite particles (mono inzeo 15/5) were predispersed in deionized water with an ULTRA-TURRAX (10 minutes at room temperature) and then added to the latex mixture (pH = 10.2; ~ 25 drc.) (Adjustment of pH Values of the latex mixture with 1% by weight KOH to pH = 10.2). In a second step, the trialkoxysilane CoatOSil MP 200 was treated at a concentration of 2.5 phr (Note: Concentration of the silane was adjusted with the concentration of the modified particles so that the concentrations of the silane in the total mixture in both cases - separate addition and addition of modified particles - is equal to the mixture added. Subsequently, the mixture was added with an anti-aging agent (0.5 phr ionol LC) and stirred for about 15 minutes at room temperature. The films were prepared by coagulation dipping method (see above), wherein the latex mixture is gently stirred during the dipping process by means of a magnetic stirrer to prevent sedimentation of the particles. The films are dried at 100 ° C for 15 minutes.
    The tear strengths of the XNBR latex films (non-sterile, not aged) were about 11 MPa for 5 phr unmodified zeolite particles, about 14 MPa for the separate addition of 5 phr unmodified zeolite particles and 2.5 phr CoatOSil MP 200 and about 17, 5 for the addition of 5phr modified zeolite particles (modified with CoatOSil MP 200).
    From the results of the tensile test, it can be concluded that the addition of CoatOSil MP 200 leads to an increase in tear strength (from 11 to 14 MPa). However, the mechanical properties of the XNBR latex films crosslinked with modified particles (17.5 MPa) could not be achieved by the separate addition. This repeatedly demonstrates the advantage of the modified particles in terms of more efficient cross-linking and good mechanical properties.
    In order to substantiate the utility of organic particles, crosslinks with modified organic carrier fillers were performed. The preparation of the crosslinked latex mixtures was carried out as described above. For the crosslinking modified fillers were used by the company Grolman chemicals Handelsgesellschaft mbH, which have been modified analogously to the Rima Sil 1200 particles with CoatOSil MP 200. Instead of the Ca silicate carrier, Grolman used a cross-linked silicone urea derivative (Rima Process).
    The tear strengths of these XNBR latex films were approximately 27.5 MPa for non-sterile and non-aged samples for 3 phr Rima Process, approximately 22.5 for 5.0 phr Rima Process, and approximately 20 MPa for 7.5 phr Rima Process, for non-sterile and aged samples at about 34 MPa for 3 phr Rima Process, at about 33 for 5.0 phr Rima Process and at about 22.5 MPa for 7.5 phr Rima Process, for sterile and non-aged samples at about 22.5 MPa for 3 phr Rima Process, at about 23 for 5.0 phr Rima Process and at about 18 MPa for 7.5 phr Rima Process and for sterile and aged samples at ca. 30 MPa for 3 phr Rima Process, with approx. 35 for 5.0 phr Rima Process and approx. 29 MPa for 7.5 phr Rima Process.
    The results of the tensile test lead to the conclusion that a successful cross-linking also succeeds with an organic support material - i. Even without ionic crosslinking, high mechanical strengths can be achieved by the covalent crosslinking of the car-boxylate groups.
    The elongation at break of these latex films was about 740% for 3 phr Rima Process, about 700% for 5.0 phr Rima Process and about 600% for 7.5 phr Rima Process, for non-sterile and non-aged samples aged samples about 720% for 3 phr Rima Process, about 690% for 5.0 phr Rima Process and about 570% for 7.5 phr Rima Process, for sterile and non-aged samples about 710% for 3 phr Rima Process, approx. 650% for 5 phr Rima Process and approx. 570% for 7.5 phr Rima Process and for sterile and aged samples approx. 660% for 3 phr Rima Process, approx. 650% for 5.0 phr Rima Process and about 560% for 7.5 phr Rima Process.
    The modulus at 50% elongation of these latex films for non-sterile and non-aged samples was about 1.3 MPa for 3 phr Rima Process, about 1.45 MPa for 5.0 phr Rima Process, and about 1.8 MPa for 7 , 5 phr Rima Process, for non-sterile and aged samples about 1.5 MPa for 3 phr Rima Process, about 1.7 MPa for 5.0 phr Rima Process and about 2 MPa for 7.5 phr Rima Process, for sterile and non-aged samples approx. 1.25 MPa for 3 phr Rima Process, approx. 1.45 MPa for 5 phr Rima Process and approx. 1.82 MPa for 7.5 phr Rima Process and for sterile and aged samples approx 1.52 MPa for 3 phr Rima Process, about 1.8 MPa for 5.0 phr Rima Process and about 2.2 MPa for 7.5 phr Rima Process.
    In the following exemplary embodiments, it should be shown that the thermal crosslinking of XNBR latex films succeeds not only with polar, water-soluble epoxide crosslinking agents but also with less polar epoxide derivatives.
    Example A Crosslinking with Bisphenol A Diglycidyl ether 3 phr of bisphenol A diglycidyl ether (Huntsman) are emulsified in 6 phr of deionized water with 0.3 phr of Tween 20. The emulsion is then added to the latex mixture (pH = 10.2; ~ 25 drc) and the latex mixture stirred for 60 minutes at room temperature. The films are produced analogously to the procedure described and the thermal crosslinking takes place in the course of drying the films in the circulating air dryer.
    Bisphenol A diglycidyl ether
    Example B - Crosslinking with a hydrogenated bisphenol A diglycidyl ether
    The preparation is analogous to Example A - only instead of the bisphenol A diglycidyl ether 3 phr or 5 phr of a hydrogenated bisphenol A diglycidyl ether (EPALLOY®5000 and EPALLOY®5001 from CVC Thermoset Specialties) are used.
    Hydrogenated bisphenol A diglycidyl ether
    Example C crosslinking with a hexahydrophthalic acid diglycidyl ether
    The preparation is analogous to Example A - only in place of the bisphenol A diglycidyl ether is a Hexahydrophtalsäurediglycidylethers (3 phr and 5 phr EPALLOY®5200 from CVC Thermoset Specialties) used
    Hexahydrophtalsäurediglycidylether
    Example D crosslinking with a 1,4-cyclohexanedimethanol diglycidyl ether
    The preparation is analogous to Example A - only in place of the bisphenol A diglycidyl ether, a 1,4-Cyclohexandimethanoldiglycidylethers (3 phr and 5 phr ERISYS ™ GE 22 from CVC Thermoset Specialties) is used.
    1,4-cyclohexanedimethanol
    The measured mechanical properties of the crosslinked XNBR latices according to Examples A-D are summarized in Table 4.
    Table 4 - Mechanical properties of thermally crosslinked XNBR latex films using different epoxides
    The embodiments describe possible embodiments of the method, and various combinations of the individual embodiments are possible with each other.
    权利要求:
    Claims (14)
    [1]
    claims
    A process for producing a prophylactic article, in particular a glove, from a (carboxylated) diene rubber, after which at least one layer of a (carboxylated) diene latex is applied to a mold, and the (carboxylated) diene latex is crosslinked with a crosslinking agent, characterized in that the crosslinking agent is immobilized on inorganic and / or organic particles to form modified particles and the modified particles are added to the (carboxylated) diene latex.
    [2]
    2. The method according to claim 1, characterized in that only the modified particles are used as crosslinking agent.
    [3]
    3. The method according to claim 1 or 2, characterized in that are used as the inorganic particles silicate-based particles.
    [4]
    4. The method according to claim 3, characterized in that the silicate-based particles are selected from a group consisting of silicates with polyvalent cations, zeolites, S1O2 and mixtures thereof.
    [5]
    5. The method according to claim 4, characterized in that a natural zeolite is used for the zeolite particles.
    [6]
    6. The method according to claim 5, characterized in that a zeolite is used as the natural zeolite, which is selected from a group consisting of clinoptilolite, chabazite, Phillipsit, Analcim and mixtures thereof.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the particles are modified with an excess of crosslinking agent to form a multi-layer structure of the crosslinking agent on the particles.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that the crosslinking of the (carboxylated) diene latex molecules is carried out thermally.
    [9]
    9. The method according to any one of claims 1 to 8, characterized in that the pH of the (carboxylated) diene latex is adjusted to a value of greater than or equal to 9.
    [10]
    10. The method according to any one of claims 1 to 9, characterized in that the crosslinking agent is selected from a group consisting of polyfunctional epoxides, polyfunctional silanes, polyfunctional siloxanes, polyfunctional thiols, and mixtures thereof.
    [11]
    11. The method according to any one of claims 1 or 3 to 10, characterized in that is used as an additional crosslinking agent is a multi-functional monomer and / or a multi-functional polymer which is added to the (carboxylated) diene latex and dissolved or emulsified in this.
    [12]
    12. The method according to claim 11, characterized in that an organic monomer and / or an organic polymer is used, which has a molecular weight between 170 g / mol and 4000 g / mol.
    [13]
    A prophylactic article, in particular a glove, comprising a layer of a (carboxylated) diene elastomer, wherein the (carboxylated) n-elastomeric (carboxylated) diene elastomer chains are covalently crosslinked via organic molecules and ionically via metal cations, characterized in that the metal cations are part of inorganic Particles are and that the organic molecules are immobilized on the inorganic particles.
    [14]
    14. Use of inorganic and / or organic particles on which a crosslinking agent is immobili Siert to form modified particles in the preparation of a prophylactic article for crosslinking a (carboxy-lated) Dienlatex.
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    同族专利:
    公开号 | 公开日
    EP3423514B1|2020-09-02|
    EP3423514A1|2019-01-09|
    JP2019512572A|2019-05-16|
    PL3423514T3|2021-04-06|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50175/2016A|AT518357B1|2016-03-04|2016-03-04|Method for producing a prophylactic article|ATA50175/2016A| AT518357B1|2016-03-04|2016-03-04|Method for producing a prophylactic article|
    ES17717059T| ES2834616T3|2016-03-04|2017-03-02|Procedure for producing a prophylactic article|
    PL17717059T| PL3423514T3|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    PT177170594T| PT3423514T|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    US16/081,481| US20190112436A1|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    JP2018546510A| JP2019512572A|2016-03-04|2017-03-02|Method of manufacturing preventive products|
    EP17717059.4A| EP3423514B1|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    PCT/AT2017/060052| WO2017147638A1|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    JP2021176386A| JP2022033725A|2016-03-04|2021-10-28|Manufacturing method of preventive products|
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