• 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, using as crosslinking agent a multifunctional monomer and / or polymer which is added to and dissolved in or emulsified in the (carboxylated) diene latex and / or in that a mercapto-functional siloxane polymer is used as crosslinking agent.
    公开号:AT518307A1
    申请号:T50176/2016
    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 chain of the (carboxylated) diene elastomer are covalently crosslinked via at least one polymer.
    In addition, the invention relates to the use of a polyfunctional monomer and / or polymer.
    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 acquires self-crosslinking properties, so that it is possible to dispense with sulfur crosslinkers and accelerators. 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.
    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 can be used that are covalently bonded to the surface of the glove. 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 a multi-functional monomer and / or polymer is used as the crosslinking agent, which is added to the (carboxylated) diene latex and dissolved in this or emulsified or dispersed therein.
    Furthermore, the object is achieved by the aforementioned prophylactic article in which the at least one polymer is a mercapto-functional siloxane polymer.
    The object of the invention is also achieved by the use of a multi-functional polymer having a number of monomer units between 2 and 50 (a molecular weight between 170 g / mol and 4000 g / mol) for adjusting the modulus of a (carboxylated) die-nelastomer prophylactic article solved.
    In addition, the object of the invention is achieved by the use of a polyfunctional organic compound as a crosslinking agent for the preparation of a prophylactic article, wherein the polyfunctional organic compound has a molecular weight between 170 g / mol and 4000 g / mol and at least two functional groups, and under basic catalysis forms hydroxy groups.
    The advantage here is that the crosslinking agent is better incorporated into the crosslinked elastomer by the chemical reaction of the crosslinking agent with the elastomeric molecules. As a result, the crosslinking agent is not or difficult to extract from the elastomer or does not migrate and only very slowly from the elastomer. By "very slowly" 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 crosslinking agent can be a polyfunctional 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 required for this. A further advantage of the process is that no precrosslinking of the (carboxylated) diene latex is required, so that continuous mixing processes can be used and processes can be accelerated. It is possible with the method an energy-efficient, sustainable and production-efficient production of hypoallergenic prophylactic articles, especially surgical and examination gloves. Due to the water solubility of the crosslinking agent, no or not necessarily an emulsifier is needed when it is introduced into the latex mixture. 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. However, admixing in the form of an emulsion is possible, especially in the case of oil-soluble monomers and / or oil-soluble polymers. In addition, the module of the prophylactic article can be better adjusted.
    According to a preferred embodiment of the method it can be provided that only the multi-functional monomer and / or polymer is 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.
    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.
    It is also possible to carry out the crosslinking of the (carboxylated) diene latex molecules photochemically by means of UV light. It can thus be improved aging resistance of the elastomer. Also with regard to high-energy radiation, the elastomer products have improved stability. This is particularly important with regard to the sterilization of medical devices with gamma radiation of importance. In addition, by this method, the use of type IV allergenic substances are also easier to avoid.
    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 epoxides, polyfunctional silanes, polyfunctional siloxanes, polyfunctional thiols. It is advantageous if they (i) have more than one epoxide function for the crosslinking of the rubber chains. Preferably, the multifunctional epoxies have a structure such that the hydrolysis product has "nourishing" properties, such as diglycidyl terminated polyethylene glycol derivative, epoxy sorbitol derivative, derivative of a sugar alcohol. Next, for example. Mono- and polysaccharides can be used with epoxy functionalities.
    In the case of carboxylated diene latexes, crosslinking with epoxides has the advantage that covalent network sites are formed via the carboxyl groups, resulting in very high tensile strengths-the covalent crosslinking via the C =C double bonds of the butadiene units, on the other hand, brings little improvement in the strengths.
    Another advantage of epoxides is the high reactivity with carboxyl groups (no additional accelerator or initiator is needed), which leads to efficient crosslinking during the drying step.
    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. Due to the high molecular weight, odor problems can also be better handled.
    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). It is further advantageous that they are still liquid even at high molecular weights (for example up to 4000 g / mol) and can therefore be more easily introduced into the latex mixture. In addition, with the siloxanes, an excessively high increase in modulus can be avoided by means of their flexible back bone.
    For better adjustment of the modulus of the prophylactic article it can be provided that an organic monomer and / or polymer is used which has a molecular weight between 170 g / mol and 4000 g / mol. It can thus be achieved a better wearing comfort for the user of the prophylactic article ,
    As already stated, it is also possible to add the crosslinking agent to the (carboxylated) diene latex as an emulsion. This is particularly advantageous if the mercapto-functional siloxane polymer is used as crosslinking agent. Due to the fine distribution of the crosslinking agent in the emulsion, a more homogeneous prophylactic article can be achieved more easily.
    As a mercapto-functional siloxane polymer, according to one embodiment, a mercapto-functional siloxane homopolymer or a copolymer of the mercapto-functional siloxane homopolymer with an acrylic siloxane can be used. In the course of tests carried out, these polymers have already been found, even at low concentrations, to be positive for the mechanical properties of the prophylactic article crosslinked therewith.
    Particularly preferred according to one embodiment of the method is a mercapto-functional siloxane homopolymer having the structural formula
    where R1 is a first moiety selected from a first group consisting of -CH3, -OH, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; - (CH 2) h, aromatic groups, -CH 2 -aromatic. Likewise, it is particularly preferred according to a further embodiment of the method, a mercapto-functional siloxane copolymer, in particular a mercapto-functional siloxane copolymer having a random arrangement of the repeating units, with the structural formula
    where R1 is a first moiety selected from a first group consisting of -CH3, -OH, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; - (CH 2) ii-, aromatic groups, -CH 2 -aromatic, and R 3 for a third unit selected from the third group consisting of alkyl groups (-CH 3, -C 2 H 5, --C 3 H 7, etc.), -CH 2 -aromatic, aromatic groups , Alkene groups (-CH = CH 2, -CH 2 CH = CH 2, etc.), methacryloxypropyl, acryloxypropyl, epoxy groups (epoxycyclohexylethyl, glycidoxypropyl). By means of these polymers, the above-mentioned effects can be further improved.
    The mercapto-functional siloxane used may also be the following dimer.
    In the course of work in the context of this invention, it has been found to be advantageous for the mercapto-functional siloxane homopolymer to be selected from a group consisting of poly (mercaptopropyl) siloxane, poly (mercaptomethylpropyl) siloxane, poly (mercaptomethylmethyl) siloxane, poly-1 (mercaptoethylmethyl) siloxane, poly (mercaptomethylethyl) siloxane, poly (mercaptopropylmethyl) siloxane, poly (mercaptomethylbenzyl) siloxane, poly (mercaptopropylbenzyl) siloxane, poly (mercaptoethylbenzyl) siloxane and / or the copolymer of the mercapto-functional siloxane homopolymer with an acrylsiloxane is selected from a group consisting of poly (mercaptomethylpropyl-co-acryloxymethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxypropylmethyl) siloxane, poly (mercaptomethylmethylcoyl) acryloxypropylethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxyethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylmethyl) siloxane, Poly (mercaptomethylmethyl-co-acryloxypropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxyethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethyl) siloxane, poly (mercaptopropylmethyl-co-acryloxymethylpropyl) siloxane. The advantage here is that these compounds have a high mercapto-equivalent number and thus a high reactivity in the crosslinking. In addition, they are liquid and can therefore easily be introduced into the system via emulsion. In addition, they are odorless and do not affect the film formation even in high concentration. Due to the polar character of the SH groups, the emulsions are also stable over a long time.
    On the one hand, the acrylate groups prevent the disulfide formation (via adjacent units) from increasing during UV crosslinking and, on the other hand, the acrylate group can also react with the rubber in the course of the thiol-ene reaction.
    According to another embodiment of the process, it can be provided that the proportion of the mercapto-functional siloxane polymer on the copolymer of the mercapto-functional siloxane polymer with an acryl siloxane is at least 20% by weight. It can thus be better achieved the advantages / effects mentioned above.
    The crosslinking agent can be added to the (carboxylated) diene latex in a proportion of from 1 phr to 10 phr, based on the total composition of the (carboxylated) diene latex. It can be better avoided that the 50% module is too high, whereby the portability of the prophylactic article would suffer. At the same time, however, with a concentration of the crosslinking agent from this range, good mechanical properties of the elastomer, such as tensile strength or maximum ductility, are obtained. It is also preferable to add at least one photoinitiator in a proportion of 0.5 phr to 5 phr. In particular, a-flydroxyalkylphenones, a-aminoalkylphenones, acylphosphine oxides, benzoin ethers, benzil ketals, α-dialkoxyacetophenones can be used as the photoinitiator.
    For a better understanding of the invention, this will be explained in more detail with reference to the following figures.
    Show it:
    Figure 1 shows the degree of swelling of crosslinked XNBR latex films over the crosslinking time at different DEPEG-500 concentrations;
    Fig. 2 shows the degree of swelling of cross-linked XNBR latex films over the cross-linking time at different GE-100 concentrations;
    Figure 3 shows the degree of swelling of crosslinked XNBR latex films over the crosslinking time at different SPE concentrations.
    Fig. 4 shows the moduli (50% elongation) of crosslinked XNBR latex films at different DEPEG-500 concentrations;
    Fig. 5 shows the moduli (50% elongation) of crosslinked XNBR latex films (non-sterile / non-aged) in DEPEG grades of different molecular weight;
    Fig. 6 shows the moduli (50% elongation) of cross-linked XNBR latex films (non-sterile / aged at 70 ° C for 7 days) for different molecular weight types of DEPEG;
    7 shows the tear strengths of UV crosslinked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (synthesis time: 3, 6 and 9 h);
    8 shows the elongations at break of UV cross-linked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (synthesis time: 3, 6 and 9 h);
    Fig. 9 shows the moduli (50% elongation) of UV cross-linked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (synthesis time: 3, 6 and 9 h);
    10 shows the tear strengths of UV cross-linked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (monomer concentration: 9 and 18% (w / v));
    Figure 11 shows the elongations at break of UV cross-linked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (monomer concentration: 9 and 18% w / v);
    Fig. 12 shows the moduli (50% elongation) of UV crosslinked NR latex films (non-sterile, not aged) at different poly (mercaptopropylmethyl) siloxane concentrations (monomer concentration: 9 and 18% w / v). 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 elastomer 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 the 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 or a polyisoprene latex or natural rubber is used to make the elastomeric layer. The nitrile-butadiene rubber latex preferably has a proportion of acrylonitrile of between 15% by weight and 40% by weight, in particular between 20% by weight and 35% by weight.
    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 for the production of an elastomer. Pre-crosslinked elastomer latices can therefore also be processed within the scope of the invention, whereby the pre-crosslinking can be effected in particular by means of the crosslinking agent mentioned in this description, which is a polyfunctional monomer and / or polymer added to and dissolved in the (carboxylated) diene latex or is emulsified or dispersed in this.
    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.
    As will be explained in more detail below, a photochemical crosslinking by means of UV light, optionally after addition of a photoinitiator, can be carried out instead of the thermal crosslinking of the elastomer molecules. The photoinitiator may be a commercially available photoinitiator and added in conventional concentrations. Reference may be made to the aforementioned US 2014/0096307 A1 and US 2014/0096308 A1, which belong to the description of the scope of the photoinitiators and their concentrations in the latex. 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 as meaning 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 producing 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 antidegradant, at least one dye, at least one antiozonate, as known per se for the manufacture 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 (carboxylated) diene elastomer latex is added to a monomeric and / or polymeric-based crosslinking agent and dissolved in the (carboxylated) diene elastomer latex. The concentration of crosslinking agent may be between 1 phr and 15 phr, in particular between 1 phr and 7.5 phr.
    In the preferred embodiment of the process, no further crosslinking agents are used, i. the crosslinking agent used is exclusively the monomer (s) soluble in the (carboxylated) diene elastomer latex and / or polymer. However, as already explained above, at least one photoinitiator can be added.
    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 epoxide (s), polyfunctional silane (s), polyfunctional siloxane (s), polyfunctional (s) 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, 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, polyglycidoxypropyltrimethoxysilane.
    Short-chain compounds are monomeric 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.
    According to another embodiment of the process, it may be provided that the mercapto-functional siloxane polymer used is a mercapto-functional siloxane homopolymer or a copolymer of the mercapto-functional siloxane homopolymer with an acrylic siloxane. In particular, a mercapto-functional siloxane homopolymer having the structural formula
    where R1 is a first moiety selected from a first group consisting of -CH3, -OH, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; - (CH 2) h, aromatic groups, -CH 2 -aromatic, and / or an acrylic siloxane having the structural formula
    where R1 is a first moiety selected from a first group consisting of -OH, -CH3, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; aromatic groups, stands.
    The mercapto-functional siloxane used may also be the following dimer.
    According to a particularly preferred embodiment of the process, the mercapto-functional siloxane homopolymer is selected from a group consisting of poly (mercaptomethylpropyl) siloxane, poly (mercaptomethylpropyl) siloxane, poly (mercaptomethylmethyl) siloxane, poly (mercaptoethylmethyl) siloxane, poly (mercaptomethylethyl) siloxane, poly (mercaptopropylmethyl) siloxane, poly (mercaptomethylbenzyl) siloxane, poly (mercaptopropylbenzyl) siloxane, poly (mercaptoethylbenzyl) siloxane, and / or the copolymer of the mercapto functional siloxane homopolymer with an acrylsiloxane is selected from a group consisting of poly (mercaptomethylpropyl-co-acryloxymethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxypropylmethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxypropylethyl) siloxane, poly (mercaptomethylmethyl -co-acryloxyethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylmethyl) siloxane, poly (mercaptomethylmeth yl-co-acryloxypropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxyethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethyl) siloxane, poly (mercaptopropylmethyl-co-acryloxymethylpropyl) siloxane.
    The proportion of the mercapto-functional siloxane polymer on the copolymer of the mercapto-functional siloxane polymer with an acrylic siloxane can be selected from a range of from 20% to 99% by weight, more preferably from 20% to 80% by weight.
    The layer thickness of the elastomer layer can be between 30 pm and 500 pm.
    Generally, the (carboxylated) diene elastomer latex may have a solids content of (carboxylated) diene elastomer between 10 drc (dry rubber content) and 60 drc.
    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 a 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) diene 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 also possible to use the (50%) module 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 process can produce a prophylactic article, especially a glove, comprising a layer of a (carboxylated) di-nelastomer wherein the (carboxylated) diene elastomeric chain of the (carboxylated) diene elastomer is covalently crosslinked via organic molecules.
    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.
    The test results for carrying out the process with polyfunctional monomers and / or polymers as crosslinking agents are reproduced below. Table 1 summarizes the educts used for this purpose.
    Table 1: materials used
    Preparation of latex blends, dipping and cross-linking
    The water-soluble crosslinker was added at varying concentrations (0.5 to 1.5 phr) of the latex mixture (pH = 10, ~ 25 drc). Subsequently, the mixture with an anti-aging agent (0.5 phr to 2 phr Ralox) was added and stirred for about 15min 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.
    The latex mixture can easily be stirred during the dipping process with the aid of a magnetic stirrer. This generally applies to the method described in this specification.
    Subsequent reactions are based on the thermal crosslinking with monomers 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 agent was accomplished 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., Kos-malska, A., Gulinski, J. Kautsch Rubber Art 2005, 58, 354). The results are shown in FIGS. 1 to 3. The crosslinking time in minutes and on the ordinates the degree of swelling are shown on the abscissa. 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 polymeric crosslinking agents.
    When using DEPEG-500, mechanical strengths in the range of 22 ± 2 MPa can be observed from a concentration of 5 phr. 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 brings a further increase in strengths 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 also been obtained with other multifunctional monomers or polymeric crosslinkers, a concentration of 1 phr to 7.5 phr of polyfunctional monomers and / or polymeric crosslinkers in the latex is generally preferred.
    Further, excellent hot air aging (7 days storage at 70 ° C) and gamma resistance (25 kGy) are observed.
    In general, it should be noted that in the course of the tests of the prophylactic article, the sterilization by gamma radiation can take place with a Co-60 source and a radiation dose of 25 kGy. Aging can generally be carried out by hot air aging at 70 ° C in a circulating air drying oven for 7 days.
    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. The results of the measurement of the 50% elongation are shown in FIG. 4. The bars are grouped therein in groups of five, with within each group of five the bars for a concentration of DEPEG-500 from left to right of 0.5 phr, 1.0 phr, 3.0 phr, 5.0 phr and 7.5 phr stand. The groups of five themselves 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. On the ordinate, the 50% modules are given in MPa.
    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
    Concentrations of 7.5 phr SPE were measured for mechanical properties 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). At a concentration of DEPEG-500 between 0.5 phr and 1.0 phr, however, only values of a maximum of about 5 MPa were measured. DEPEG-500 is therefore preferably used in an amount of 5 phr to 7.5 phr.
    In addition, when SPE is used as the water-soluble polymeric crosslinking agent, a marked increase in tension at 50% elongation is observed, which is detrimental to the comfort of wearing the elastomeric glove. At 7.5 phr SPE, values in the range of 1.6 to 1.8 MPa are obtained. SPE is therefore preferably used in a concentration of 0.5 phr to 5 phr.
    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.
    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.
    The measurement results of this investigation are shown in FIGS. 5 and 6. The concentration of crosslinking agent in phr is plotted on the abscissa and the measured stresses at 50% strain in MPa are plotted on the ordinates.
    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.
    Selected examples of the photochemical crosslinking of elastomer latices are given below. Table 2 summarizes the educts used for this purpose.
    Table 2: materials used
    The preparation of the polymeric siloxane crosslinking agent can be carried out as follows. 0.1 M HCl (aq.) And ethanol are initially charged, heated to 50 ° C and rinsed with a continuous Ish stream. Subsequently, the corresponding siloxane monomers (see Table 2) are added in selected concentrations of 5% (w / v) and 40% (w / v). After 3 to 9 hours at 50 ° C, the reaction is stopped by cooling and the oily product is washed with deionized water and extracted with chloroform. The solvent is removed under vacuum at completion and the product stored under N 2 atmosphere.
    The reaction schemes of the synthesized homopolymers and copolymers are listed below.
    Synthesis of poly (mercaptopropyl) siloxane:
    Synthesis of poly (mercaptanethylmethyl) siloxane:
    Synthesis of poly (mercaptopropylmethyl) siloxane
    Synthesis of poly (mercaptopropylmethyl-co-acryloxypropylmethyl) siloxane
    The molecular weight distribution of the siloxanes was determined by gel permeation chromatography (universal calibration with polystyrene standards). The following results were obtained: - poly (mercaptopropylmethyl) siloxane (3 hours reaction time) molecular weight: 200 g / mol - 700 g / mol (2 to 5 units) - poly (mercaptopropylmethyl) siloxane (9 hours reaction time) molecular weight: 200 1,400 g / mol (2 to 10 units) - poly (mercaptopropylmethyl-co-acryloxypropylmethyl) siloxane (3 hours reaction time)
    Molecular weight: 200-1,300 g / mol
    Preparation of Latex Films and UV Crosslinking with Polymeric Siloxane Crosslinking Agents
    Synthesized polymeric crosslinkers are emulsified at different concentrations (1 to 4 phr) with Lucirin TPO-L (1 phr) in deionized water with Tween 20 (0.1 phr) and then added to NR latex (40 drc). The latex mixture is treated with an anti-aging agent (0.5 phr ionol LC) and stirred for two hours at room temperature. Subsequently, the films are produced by means of the following coagulation dip method:
    Washing the ceramic molds and degreasing with acetone
    - Preheat the ceramic molds for at least 10 minutes in a drying oven at 120 ° C
    - Dipping the mold for 30 s in the coagulation bath at 70 ° C
    - Dry the mold for at least 1 min in a drying oven at 120 ° C - Dipping the mold in the NR latex mixture for 20s
    - Dry for 20 min in a drying oven at 120 ° C - Peel off the film
    The UV crosslinking of the NR latex films took place in the course of UV exposure of the dried films (post-curing) with a UV emitter from Fusion UV Systems Inc. The UV exposure was carried out under air with a Ga-doped Hg emitter a lamp power of 60% and a belt speed of 3.5 m / min. With three passes, the radiation dose is 15.6 J / cm2.
    It should be noted that the parameters given are not to be understood as limiting, but merely to show a way of producing the prophylactic articles on a laboratory scale, for example. In the large-scale application, slightly different parameters may be required, but these can be found by fewer attempts.
    Subsequent reaction mechanism is based on the photochemical crosslinking with polymeric Siloxanvernetzungsmitteln.
    In general, the following parameters can be used for the UV crosslinking: IR latices parameter for UV precrosslinking in the falling film reactor: radiator power at 800 W -1000 W (800 W results in a mean radiation flux of ~ 500 mW / cm 2), double exposure pass, conveying speed (latex mixture at 1.1 l / min to 1.5 l / min, solids (latex) at 40% drc, photoinitiator concentration at 0.5 phr to 2phr, thiol concentration at 0.5 phr to 2 phr. NR latices parameter for UV precrosslinking in the falling film reactor: radiator power at 2000 W-3500 W (3000 W gives a mean radiation flux of ~ 1690 mW / cm 2) double exposure pass, conveying speed (latex mixture) at 1.1 l / min to 1, 5 l / min, solids content (latex) at 40% drc., Photoinitiator concentration at 0.5 phr to 2phr, thiol concentration at 1 phr to 5 phr.
    General parameters for UV postcrosslinking: Residual moisture content of the films preferably below 20%. Post-dosing of 0.5 phr to 5 phr of photoinitiator and 1 phr to 7.5 phr of thiol, irradiation dose between 1 J / cm 2 and 25 J / cm 2 (240 nm -420 nm wavelength range).
    The exposure is preferably carried out under air with a Ga-doped Hg emitter.
    The structure of the polymeric crosslinkers was determined by FT-IR spectroscopy and by thermogravimetry (TGA). In the FT-IR spectra of the mercapto-functional siloxane homopolymers poly (mercaptopropyl) siloxane, poly (mercaptomethylpropyl) siloxane and poly (mercaptomethylmethyl) siloxane, a significant reduction of the Si-O-CFb band at ca. 2830 cm'1 and the formation of OFI- Groups (about 3370 cm-1) are observed, which indicate a successful condensation reaction of Siloxanmonore (Alkoxysilanmo- monomers) infer. Further, the broadening of the Si-O band at about 1060 cnrr1 indicates the formation of a polymeric compound. The characteristic SH band (about 2558 cm-1) is weak, since the infrared bands of thiol groups generally have a very low intensity. In the FT-IR spectrum of the copolymer poly (mercaptopropylmethyl-co-acryloxymethylpropyl) siloxane are in addition the characteristic IR bands of the acrylate group (C = 0 bands at 1727 cm'1 and C = C bands at 1637 and 1622 cm'1 ) detectable.
    In the course of the TGA investigations it could be shown that the homopolymers and copolymers, depending on the structure, are stable up to a temperature range of 240 ° C to 270 ° C and then show a multi-stage degradation.
    To determine the reactivity of the polymeric crosslinking agents, a 2% by weight solution of polyisoprene standard in chloroform was prepared and added with 1 phr Lucirin TPO-L and 5 phr of the corresponding thiol. The mixture was knife-coated onto CaF 2 plates, the solvent was evaporated and the exposed layers were then exposed with a UV lamp (OmniCure Series 1000, EXFO's high pressure lamp, full power: 100 W). After different exposure times, IR spectra were recorded and the decrease in the normalized C = C band (835 cm-1) was recorded over the exposure time. Compared to the commercially available high molecular weight thiol dipen-taerythritolhexa (3-mercaptopropionate) (THIOCURE® Di-PETMP, Bruno Bock Thiochemicals), the siloxane polymers have a significantly higher reactivity in the crosslinking. While using THIOCURE® Di-PETMP the relative decrease of the C = C bands after an exposure time of 150s is about 5%, a decrease in the range of 12% can be achieved when using poly (mercaptopropylmethyl) siloxane.
    The reactivity of the polymeric crosslinkers in the UV-initiated thiol-ene reaction was confirmed in further experiments. For this purpose, the crosslinking agents (1 phr) were mixed together with a photoinitiator (1 phr Lucirin TPO-L) in a polyisoprene standard solution (2 wt .-% in chloroform) and then thin films (40 pm), dried, patterned exposed and in chloro - developed form. Similar to a negative resist, the exposed areas of the layer are crosslinked by the thiol-ene reaction, and in the subsequent development in chloroform, only the unexposed areas could be dissolved and removed. This experiment was performed with a Mask Aligner at a very low exposure dose (~ 20 mW / cm2, 80 s) to minimize the influence of the direct C-C linkage of the polymer chains by the photoinitiator radicals. The results show that even a low concentration (1 phr) of the polymeric crosslinkers is sufficient to obtain a very high spatially resolved crosslinking of the polyisoprene standard. The results thus confirm the high reactivity and efficiency of the synthesized polymeric crosslinkers in the thiol-ene reaction.
    Due to its chemical structure (high concentration of free Si-OH groups), poly (mercaptopropyl) siloxane can crosslink in the course of storage (even under an inert atmosphere) via a condensation reaction. The polymeric compound therefore has only a limited shelf life (about 1 week). UV cross-linked NR latex films (before aging and gamma sterilization) with 1 and 2phr cross-linking agents have a tensile strength of 12 MPa - 15 MPa.
    In order to minimize possible secondary reactions (especially cross-linking) during the storage of the polymeric crosslinking agents, disiloxane monomers were used in further synthetic approaches. The polymeric compound is characterized by the lower concentration of free Si-OH groups by a much higher storage stability and it is also observed over a storage of 1 month (under an atmosphere) no change in viscosity. The influence of different parameters (including reaction time, monomer content) in the synthesis on the corresponding mechanical strengths and aging resistance of NR latex films was further investigated.
    In the first step, the synthesis of poly (mercaptopropylmethyl) siloxane was stopped at a constant monomer concentration in the reaction mixture (9% (w / v)) after different reaction times (3, 6 and 9 hours), worked up the polymeric product and corresponding cross-linking experiments performed ,
    At a crosslinker concentration of 1 phr, the lower reaction time polymer (3 hours) has the better mechanical strengths (20 ± 2 MPa). However, at higher concentrations (2 phr) of the polymeric crosslinkers, only a slight difference in mechanical strengths can be observed and values are in the range of 22 to 24 MPa. The results are shown in FIGS. 7 to 9.
    In further work, the monomer concentration in the synthesis was varied with a constant reaction time of 3 hours (9 and 18% (w / v)). While at lower monomer concentrations (9 (w / v)) an increase in tear strength (from 20 to 26 ± 2 MPa) can be observed with increasing crosslinker concentration in the latex mixture (from 1 to 3 phr), at a higher monomer concentration (18%). (w / v)) achieved an optimum at 2 phr of the crosslinker in the latex mixture (27 ± 2 MPa). The results of this study are shown in FIGS. 10 to 12.
    In addition, NR latex films were prepared at higher levels of polymeric crosslinkers, UV exposed, and the effect of crosslinker concentration on mechanical properties examined. As the polymeric crosslinking agent, poly (mercaptopropylmethyl) siloxane (monomer concentration: 18% (w / v), reaction time: 3 hours) was selected. The results suggest that a further increase in crosslinker concentration from 3 phr to 4 phr does not result in any significant improvement in tear strengths. Although an increase in stress at 50% elongation can be achieved, indicating a higher degree of crosslinking, the tear strengths remain in the range of 25 MPa.
    In a further step, a polymeric thiol crosslinking agent having a shorter intermediate group (between the thiol group and the polymeric main chain) was synthesized. Instead of the propyl group, a methyl group was chosen. The monomer concentration in the synthesis was 9% (w / v) and the reaction time three
    Hours. Also, this polymeric compound is storage stable and no viscosity changes can be observed over a shelf life of one month.
    With poly (mercaptomethylmethyl) siloxane as crosslinking agent, in comparison to poly (mercaptopropylmethyl) siloxane at the same crosslinker concentrations (1 phr or 2 phr), higher mechanical strengths in the UV crosslinking of NR latex tend to be achieved. The tear strengths for non-sterile and non-aged films at a concentration of poly (mercaptopropylmethyl) siloxane of 1 phr is about 23 MPa and at 2 phr about 26 MPa. The 50% moduli for non-sterile and non-aged films at a concentration of poly (mercaptopropylmethyl) siloxane of 1 phr is about 0.45 MPa and at 2 phr about 0.5 MPa.
    In addition to the mercapto-functional homopolymers, copolymers with acryloxypropylmethyl units have also been synthesized and used as crosslinking agents in the UV crosslinking of NR latex. On the one hand, the formation of disulphides (as a side reaction of the thiol-ene reaction) should be prevented by the acrylate groups as the second monomer unit, and on the other hand a reactive group (acrylates) should be available for the attachment of the polymeric crosslinking agent to the rubber chain. The total concentration of both monomers in the synthesis was 9% (w / v) and the reaction time was three hours. Also, this polymeric compound is storage stable and no viscosity changes can be observed over a shelf life of one month. Compared with the corresponding homopolymer (poly (mercaptopropylmethyl) siloxane), with the copolymer, significantly higher tear strengths (up to 30 MPa) can be achieved with the same crosslinking agent concentration in the latex mixture.
    In further work, the influence of the comonomer composition on the mechanical properties was investigated. Here, the concentration of 3-Acryloxypropylmethylsiloxan was doubled from 8.4 to 16.8% (mol / total mol). The results of the tensile test show that with 2 phr of P (MPMS-co-APMS) an increase in the acrylate units in the polymer chain is associated with a slight reduction of about 8% of the mechanical properties.
    As a reference, an acrylate homopolymer was also synthesized (analogously to the synthesis of the crosslinking agents mentioned above) and used as a crosslinking agent. Due to the high reactivity of the acrylate groups, photochemical crosslinking is achieved via direct C-C linkage with the isoprene units. Although the successful patterned exposure of polyisoprene films with poly (acryloxypropylmethyl) siloxane as the crosslinking agent suggests that the reactivity in UV crosslinking is sufficiently high, the mechanical properties of corresponding NR latex films (with 1 phr and 2 phr crosslinkers) are significantly lower ( 14 to 17 MPa) compared to the mercapto-functional homo- and copolymers. In addition, the films are characterized by insufficient aging resistance (7 days hot air aging at 70 ° C) (<3 MPa and strong yellowing).
    In further experiments, the influence of pre- or post-crosslinking on the crosslinking of NR latex and IR latex with poly (mercaptomethylmethyl) siloxane as a polymeric crosslinking agent was investigated.
    scorching:
    Synthesized polymeric crosslinkers (0.5 phr) were emulsified with Lucirin TPO-L (0.5 phr) in deionized water with Tween 20 (0.1 phr) and then NR-latex (40 drc) or IR Latex (40 drc., Kraton). The latex mixture was stirred for 2 hours at room temperature. Subsequently, the respective latex mixture was poured into a Petri dish (about 1 mm layer thickness) and exposed with a UV lamp from Fusion UV Systems Inc. The NR latex blends were irradiated in air with a Ga doped Hg emitter at a lamp power of 60% and a belt speed of 3.5 m / min in four passes (equivalent to a radiation dose of 20.8 J / cm 2). The IR latex mixtures were irradiated under air with a Ga-doped Hg emitter at a lamp power of 60% and a belt speed of 3.5 m / min in two passes (corresponding to a radiation dose of 10.4 J / cm 2). ,
    In the preparation of pre-crosslinked films (without subsequent post-crosslinking), the latex mixture was mixed after the pre-crosslinking with the anti-aging agent (0.5 phr ionol LC) and stirred for 2 hours at room temperature. Subsequently, the latex films were dipped by means of coagulation dip. The following work steps are carried out: - Washing the ceramic molds and degreasing with acetone
    - Preheat the ceramic molds for at least 10 minutes in a drying oven at 120 ° C
    - Dip the mold for 30 seconds in the coagulation bath at 70 ° C
    - Dry the mold for at least 1 minute in a drying oven at 120 ° C - Dip the mold into the NR latex mixture for 20 seconds
    - Dry for 20 minutes in a drying oven at 120 ° C - Peel off
    postcrosslinking:
    Optionally, a post-crosslinking was carried out. The respective latex mixtures (pre-crosslinked or not pre-crosslinked) were mixed with an emulsion consisting of the synthesized polymeric crosslinking agent (2 phr), Lucirin TPO-L (1 phr), deionized water (2 phr) and Tween 20 (0.1 phr). , offset. Subsequently, the latex mixture with an anti-aging agent (0.5 phr ionol LC) was added and stirred for 2 hours at room temperature.
    Corresponding films were made by the coagulation dipping method and the post-crosslinking was carried out by UV exposure of the dried films (post-curing) with a UV-emitter from Fusion UV Systems Inc. Both NR latex films and IR latex films were air-exposed a Ga-doped Hg emitter irradiated at a lamp power of 60% and a belt speed of 3.5 m / min in three passes (corresponds to a
    Radiation dose of 15.6 J / cm2).
    The photochemical cross-linking of the NR latex showed that the highest mechanical strengths can be achieved by postcrosslinking. The tear strength of the NR latex films (non-sterile, not aged) was about 22.5 MPa for the pre-crosslinked sample, about 18 MPa for the pre-crosslinked and post-crosslinked sample and about 25 MPa for the exclusively post-crosslinked sample. This result is surprising in that the pre- and post-crosslinked sample had the lowest tear strength.
    A similar trend is also observed in the UV precrosslinking of IR latex. Here, the tear strength of precrosslinked IR latex films is in the range of 3.5 MPa. In contrast to NR latex films, however, a combined increase in the tear strength to 16 MPa is possible by combined pre- and post-crosslinking.
    For further evaluation of the polymeric crosslinkers, additional mercaptopolymers were synthesized. For this purpose, for a more controlled polymerization (preparation of polymers having a lower polydispersity index), the preparation of poly (mercaptomethylmethyl) siloxane and poly (mercaptopropylmethyl-co-acryloxypropylmethyl) siloxane was carried out in the presence of 2 phr or 3 phr of methoxytrimethylsilane as the terminating reagent. The synthesis was carried out analogously to the above-described synthesis, wherein in addition 2 phr or 3 phr methoxytrimethylsilane (Sigma-Aldrich) was added to the reaction mixture.
    The tear strengths of UV postcrosslinked NR latex films (non-sterile, not aged) are consistently between 25 MPa and 27 MPa.
    For the determination of the extractable crosslinking agent concentration, postcrosslinked NR latex films were extracted by means of a Soxhlet extraction (10 hours / toluene). The solvent was removed by rotary evaporation and the extract dried in a vacuum oven to constant weight at 35 ° C and 100 mbar.
    By means of C / H / N / S, the extractable S compounds (thiols and proteins of the NR latex) were determined in a triple determination.
    The results of the elemental analysis show a significantly lower extractability (75%) of the crosslinking agent compared to low molecular weight thiols (such as trimethylolpropane trimercaptopropionate, TMPMP).
    Table 3 - S concentration in the extract of UV postcrosslinked NR latex films
    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 (17)
    [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 used is a polyfunctional monomer and / or polymer which is added to and dissolved in or emulsified in the (carboxylated) diene latex and / or in that a mercapto-functional siloxane polymer is used as crosslinking agent.
    [2]
    2. The method according to claim 1, characterized in that only the multi-functional monomer and / or polymer is used as crosslinking agent.
    [3]
    3. The method according to claim 1 or 2, characterized in that the crosslinking of the (carboxylated) diene latex molecules is carried out thermally and / or photochemically by means of ultraviolet radiation.
    [4]
    4. The method according to any one of claims 1 to 3, characterized in that the pH of the (carboxylated) diene latex is adjusted to a value of greater than or equal to 9.
    [5]
    5. The method according to any one of claims 1 to 4, characterized in that the crosslinking agent is selected from a group consisting of polyfunctional epoxides, polyfunctional silanes, polyfunctional siloxanes, polyfunctional thiols, and mixtures thereof.
    [6]
    6. The method according to any one of claims 1 to 5, characterized in that an organic monomer and / or polymer is used which has a molecular weight between 170 g / mol and 4000 g / mol.
    [7]
    7. The method according to any one of claims 1 to 6, characterized in that the mercapto-functional siloxane polymer is added to the (carboxylated) diene latex as an emulsion.
    [8]
    8. The method according to any one of claims 1 to 7, characterized in that is used as the mercapto-functional siloxane polymer, a mercapto-functional siloxane homopolymer or a copolymer of the mercapto-functional siloxane homopolymer with an acrylic siloxane.
    [9]
    9. The method according to claim 8, characterized in that a mercapto-functional siloxane homopolymer having the structural formula

    where R1 is a first moiety selected from a first group consisting of -CH3, -OH, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; - (CH 2) h, aromatic groups, -CH 2 -aromatic.
    [10]
    10. The method according to claim 8, characterized in that a mercapto-functional siloxane copolymer, in particular a mercapto-functional siloxane copolymer having a random arrangement of the repeating units, having the structural formula

    where R1 is a first moiety selected from a first group consisting of -CH3, -OH, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; - (CH 2) h, aromatic groups, -CH 2 -aromatic, and R 3 represents a third moiety selected from the third group consisting of alkyl groups, -CH 2 -aromatic, aromatic groups, alkene groups, methacryloxypropyl, acryloxypropyl, epoxy groups.
    [11]
    11. The method according to any one of claims 8 to 10, characterized in that an alkoxyacrylsilane having the structural formula

    where R1 is a first moiety selected from a first group consisting of -OH, -CH3, -C2H5, -C3H7, aromatic groups, R2 for a second moiety selected from the second group consisting of -CH2, C2H4, C3H6; aromatic groups.
    [12]
    12. The method according to any one of claims 8 to 10, characterized in that the mercapto-functional siloxane homopolymer is selected from a group consisting of poly (mercaptopropylmethyl) siloxane, poly (mercaptopropylmethyl) siloxane, poly (mercaptomethylmethyl) siloxane, poly (mercaptoethylmethyl ) siloxane, poly (mercaptomethylethyl) siloxane, poly (mercaptopropylmethyl) siloxane, poly (mercaptomethylbenzyl) siloxane, poly (mercaptopropylbenzyl) siloxane, poly (mercaptoethylbenzyl) siloxane, and / or the copolymer of the mercapto functional siloxane homopolymer with an acrylsiloxane from a group consisting of poly (mercaptopropylmethyl-co-acryloxypropylmethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxypropylmethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxypropylethyl ) siloxane, poly (mercaptomethylmethyl-co-acryloxyethylpropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethylmethyl) siloxane, poly (mercapt tomethylmethyl-co-acryloxypropyl) siloxane, poly (mercaptomethylmethyl-co-acryloxyethyl) siloxane, poly (mercaptomethylmethyl-co-acryloxymethyl) siloxane, poly (mercaptopropylmethyl-co-acryloxymethylpropyl) siloxane.
    [13]
    13. The method according to any one of claims 8 to 11, characterized in that the proportion of the mercapto-functional siloxane polymer to the copolymer of the mercapto-functional siloxane polymer with an acrylic siloxane at least 20 wt .-% is.
    [14]
    14. The method according to any one of claims 1 to 12, characterized in that crosslinking agent is added to the (carboxylated) diene latex in an amount of 1 phr to 10 phr, based on the total composition of the (carboxylated) diene latex.
    [15]
    A prophylactic article, in particular a glove, comprising a layer of a (carboxylated) diene elastomer wherein the (carboxylated) n-elastomeric (carboxylated) diene elastomer covalent crosslinks via at least one polymer, characterized in that the at least one polymer is a mercapto-functional siloxane polymer ,
    [16]
    16. Use of a polyfunctional polymer having a number of monomer units between 2 and 50 for adjusting the modulus of a (carboxylated) diene elastomer prophylactic article.
    [17]
    17. Use of a polyfunctional organic compound having a molecular weight between 170 g / mol and 4000 g / mol, having at least two functional groups which forms hydroxy groups under basic catalysis, as a crosslinking agent for preparing a prophylactic article.
    类似技术:
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    同族专利:
    公开号 | 公开日
    EP3632965A1|2020-04-08|
    US10808046B2|2020-10-20|
    EP3423515B1|2020-08-26|
    EP3423515A1|2019-01-09|
    PT3423515T|2020-11-24|
    ES2833935T3|2021-06-16|
    JP2019518808A|2019-07-04|
    US20190092879A1|2019-03-28|
    AT518307B1|2020-04-15|
    WO2017147639A1|2017-09-08|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    ATA50176/2016A|AT518307B1|2016-03-04|2016-03-04|Method of making a prophylactic article|ATA50176/2016A| AT518307B1|2016-03-04|2016-03-04|Method of making a prophylactic article|
    PCT/AT2017/060053| WO2017147639A1|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    PT177170602T| PT3423515T|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    EP19210944.5A| EP3632965A1|2016-03-04|2017-03-02|Method for producing a prophylactic item|
    EP17717060.2A| EP3423515B1|2016-03-04|2017-03-02|Method for producing a prophylactic article|
    ES17717060T| ES2833935T3|2016-03-04|2017-03-02|Procedure for manufacturing a prophylactic article|
    JP2018546527A| JP2019518808A|2016-03-04|2017-03-02|Method of manufacturing preventive products|
    US16/081,486| US10808046B2|2016-03-04|2017-03-02|Method for producing a prophylactic article|
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