Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
  • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
  • D06M23/16—Processes for the non-uniform application of treating agents, e.g. one-sided treatment; Differential treatment
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06Q—DECORATING TEXTILES
  • D06Q1/00—Decorating textiles
  • D06Q1/04—Decorating textiles by metallising
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F41—WEAPONS
  • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
  • F41H5/00—Armour; Armour plates
  • F41H5/02—Plate construction
  • F41H5/04—Plate construction composed of more than one layer
  • F41H5/0442—Layered armour containing metal
  • F41H5/0457—Metal layers in combination with additional layers made of fibres, fabrics or plastics
  • F41H5/0464—Metal layers in combination with additional layers made of fibres, fabrics or plastics the additional layers being only fibre- or fabric-reinforced layers
• • A—HUMAN NECESSITIES
  • A41—WEARING APPAREL
  • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
  • A41D31/00—Materials specially adapted for outerwear
  • A41D31/04—Materials specially adapted for outerwear characterised by special function or use
  • A41D31/24—Resistant to mechanical stress, e.g. pierce-proof
  • A41D31/245—Resistant to mechanical stress, e.g. pierce-proof using layered materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T156/00—Adhesive bonding and miscellaneous chemical manufacture
  • Y10T156/10—Methods of surface bonding and/or assembly therefor
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T29/00—Metal working
  • Y10T29/49—Method of mechanical manufacture
  • Y10T29/49826—Assembling or joining
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12014—All metal or with adjacent metals having metal particles
  • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
  • Y10T428/12049—Nonmetal component

Definitions

• the present invention relates to a method for producing multilayer materials according to the invention and their use, for example for protective clothing and for mechanically stressed articles.
• Protective clothing such as sports clothing for fencing, and textiles for mechanically heavily stressed systems, such as car seats, must protect against various mechanical effects. These include blunt bats, stitches and cuts as well as thrown objects.
• Another method is to incorporate metal foils into textile composites.
• a disadvantage of this method is that a metal foil with a crack or punctiform damage generally loses drastically in mechanical stability.
• the multilayer materials according to the invention also referred to below as systems according to the invention, comprise at least two metallized layers on at least one textile layer, for example two textiles metallized on one side or a double-sided metallized textile.
• multilayer materials according to the invention may comprise three, four or five textiles metallized one-sidedly in each case.
• multi-ply materials according to the invention may be three, four or five, each double-sided metallized textile include.
• multilayer materials according to the invention may comprise at least one unilaterally metallized and at least one double-sided metallized textile.
• the multilayer material according to the invention is characterized in that it comprises, as outer layer (outer layer), in each case a layer of textile which has not been treated according to steps (A) and (B) or which in each case on the inner side after step ( A) and (B) are treated, but not on the outside.
• the initially defined method is based on textile, in particular flat textile or three-dimensionally configured textile material, for example a knitted fabric, a knitted fabric (knit fabric) or preferably a woven fabric or a nonwoven fabric (non-woven).
• Textile in the sense of the present invention may be stiff or preferably flexible.
• textile is a combination of different textiles that may be joined together.
• combinations of fabrics and knitwear may be mentioned.
• Textile in the sense of the present invention may be natural fibers or synthetic fibers or mixtures of natural fibers and synthetic fibers.
• Natural fibers include, for example, cotton, wool or flax.
• synthetic fibers include polyamide, polyester, modified polyester, polyester blends, polyamide blends, polyacrylonitrile, triacetate, acetate, polycarbonate, polypropylene, polyvinyl chloride and polyester microfibers, preferably polyester and blends of cotton with synthetic fibers, especially blends of cotton and polyester.
• flat textiles made of carbon fibers, glass fibers or aramid fibers are preferred.
• textile is a part of a composite.
• a layer of textile can be connected to another layer of textile, for example glued, quilted, laminated, sewn or needled, in each case over the entire surface, partially or also punctiform.
• a layer of textile can be laminated over its entire area with a different layer of textile, adhesively bonded in spots, partially sewn or quilted.
• a textile material is connected to another material, so the textile surface from which one starts, laminated on a film for example, a polyester film, a polyolefin film, in particular a polyethylene film or a polypropylene film, furthermore a polyamide film or a polyurethane film.
• a film for example, a polyester film, a polyolefin film, in particular a polyethylene film or a polypropylene film, furthermore a polyamide film or a polyurethane film.
• textile may be a coated textile surface coated, for example, with binders such as polyurethane binders, polyacrylate binders or styrene-butadiene latex.
• binders such as polyurethane binders, polyacrylate binders or styrene-butadiene latex.
• a formulation containing at least one metal powder (a) is applied to at least two textile surfaces in a pattern or area in step (A).
• the application can be done, for example, by knife coating, spraying, roll coating, dipping and in particular by printing or printing.
• the application to at least two textile surfaces can, for example, be done by applying formulation (A) to the front and the back of the same textile or by applying formulation (A) to one or both sides of two or more textiles. It is preferred to apply at least two textiles in each case one-sided formulation (A).
• the formulation containing at least one metal powder (a) may preferably be aqueous formulations, in particular aqueous liquors or, more preferably, a printing formulation.
• step (A) at least two textile surfaces are printed, each with a printing formulation which may be different or preferably the same, preferably with an aqueous printing formulation containing at least one metal powder (a).
• aqueous printing formulations are printing inks, e.g. As gravure inks, offset inks, flexographic inks, screen inks, printing inks such.
• Metal powder (a) is powdered metal, pure or as a mixture or alloy, excluding the alkali metals and the alkaline earth metals Be, Ca, Sr and Ba. Likewise, of course, the radioactive metals are excluded.
• Metal powder (a) may be selected, for example, from powdered Al, Zn, Ni, Cu, Ag, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi, for example, pure or as mixtures or in the form of powdered alloys of said metals with each other or with other metals.
• suitable alloys are CuZn, CuSn, CuNi, SnPb, SnBi, SnCu, NiP, ZnFe, ZnNi, ZnCo and ZnMn.
• Preferably usable metal powders (a) are iron powder and / or copper powder, most preferably iron powder.
• the metal powder selected is (a) carbon, in the modification as graphite in particulate form, carbon black or carbon nanotubes.
• This variant is particularly preferred when working in step (B) described below with external voltage source .
• Carbon in the modification graphite in particulate form, carbon black or carbon nanotubes is in the context of the present invention under the term metal powder (a) with includes.
• the metal powder selected is (a) a mixture of powdered Al, Zn, Ni, Cu, Ag, Sn, Co, Mn, Fe, Mg, Pb, Cr and Bi, in particular iron powder on the one hand and carbon in the graphite modification in particulate form, carbon black or carbon nanotubes on the other hand.
• metal powder (a) has an average particle diameter of from 0.01 to 100 ⁇ m, preferably from 0.1 to 50 ⁇ m, particularly preferably from 1 to 10 ⁇ m (determined by laser diffraction measurement, for example on a Microtrac X100 device).
• metal powder (a) is characterized by its particle diameter distribution.
• the value d 10 can be in the range of 0.01 to 5 ⁇ m, the value for d 50 in the range of 1 to 10 ⁇ m and the value for d 90 in the range of 3 to 100 ⁇ m, where d 10 ⁇ d 50 ⁇ d 90 .
• no particle has a larger diameter than 100 microns.
• Metal powder (a) can be used in passivated form, for example in an at least partially coated (“coated") form.
• suitable coatings include inorganic layers such as the oxide of the metal in question, SiO 2 or SiO 2 .alpha., Or phosphates, for example, of the metal in question.
• the particles of metal powder (a) can in principle have any desired shape, for example acicular, cylindrical, plate-shaped or spherical particles can be used; spherical and plate-shaped particles are preferred.
• acicular, cylindrical, plate-shaped and spherical may refer to idealized shapes, respectively.
• metal powders (a) with spherical particles are used, preferably predominantly with spherical (spherical) particles, very particularly preferably so-called carbonyl iron powders with spherical particles.
• metal powders (a) are used, which are a mixture of spherical (spherical) particles, most preferably so-called carbonyl iron powder with spherical particles, and platelet-shaped particles, in particular platelet-shaped copper particles.
• Metal powder (a) can, in one embodiment of step (A), be applied and preferably printed so that the particles of metal powder are so close that they are already capable of conducting electrical current. In another embodiment of step (A), metal powder (a) may be applied, preferably by printing, that the particles of metal powder (a) are so far apart that they are not capable of conducting the electrical current.
• metal powders (a) are known per se. It is possible, for example, to use common commercial goods or metal powder (a) prepared by processes known per se, for example by electrolytic deposition or chemical reduction from solutions of salts of the metals concerned or by reduction of an oxidic powder, for example by means of hydrogen, by spraying or atomizing a molten metal, in particular in cooling media, for example gases or water.
• metal powder (a) which has been prepared by thermal decomposition of iron pentacarbonyl, also called carbonyl iron powder in the context of the present invention.
• the preparation of carbonyl iron powder by thermal decomposition of, in particular iron pentacarbonyl Fe (CO) 5 is, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A14, page 599 , described.
• the decomposition of iron pentacarbonyl can be carried out, for example, at atmospheric pressure and, for example, at elevated temperatures, eg. B. in the range of 200 to 300 ° C, z. B. in a heatable decomposer comprising a tube of a refractory material such as quartz glass or V2A steel in a preferably vertical position, by a heating device, For example, consisting of heating bands, heating wires or from a heating medium flowed through by a heating jacket, is surrounded.
• a heating device For example, consisting of heating bands, heating wires or from a heating medium flowed through by a heating jacket, is surrounded.
• the mean particle diameter of carbonyl iron powder can be controlled by the process parameters and reaction behavior in the decomposition in wide ranges and is (number average) usually from 0.01 to 100 .mu.m, preferably from 0.1 to 50 .mu.m, more preferably from 1 to 8 microns.
• Formulations used according to the invention may contain at least one binder (b), also called binder (b), preferably at least one aqueous dispersion of at least one film-forming polymer, for example polyacrylate, polybutadiene, copolymers of at least one vinylaromatic with at least one conjugated diene and optionally other comonomers, for example styrene-butadiene binders.
• binder (b) preferably at least one aqueous dispersion of at least one film-forming polymer, for example polyacrylate, polybutadiene, copolymers of at least one vinylaromatic with at least one conjugated diene and optionally other comonomers, for example styrene-butadiene binders.
• Other suitable binders (b) are selected from polyurethane, preferably anionic polyurethane, or ethylene (meth) acrylic acid copolymer. Binder (b) can also be referred to as binder (b) in
• Suitable polyacrylates for the purposes of the present invention as binders (b) are obtainable, for example, by copolymerization of at least one (meth) acrylic acid C 1 -C 10 -alkyl ester, for example methyl acrylate, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, with at least one further comonomer, for example a further (meth) acrylic C 1 -C 10 -alkyl ester, (meth) acrylic acid, (meth) acrylamide, N-methylol (meth) acrylamide, glycidyl (meth) acrylate or a vinyl aromatic compound such as styrene.
• at least one (meth) acrylic acid C 1 -C 10 -alkyl ester for example methyl acrylate, ethyl acrylate, n-butyl acrylate, n-buty
• suitable preferably anionic polyurethanes in the context of the present invention are obtainable, for example, by reacting one or more aromatic or preferably aliphatic or cycloaliphatic diisocyanate with one or more polyester diols and preferably one or more hydroxycarboxylic acids, eg. B hydroxyacetic acid, or preferably dihydroxycarboxylic acids, for example 1,1-dimethylolpropionic acid, 1,1-dimethylolbutyric acid or 1,1-dimethylolethanoic acid.
• hydroxycarboxylic acids eg. B hydroxyacetic acid
• dihydroxycarboxylic acids for example 1,1-dimethylolpropionic acid, 1,1-dimethylolbutyric acid or 1,1-dimethylolethanoic acid.
• Ethylene (meth) acrylic acid copolymers which are particularly suitable as binders (b) are, for example, by copolymerization of ethylene, (meth) acrylic acid and optionally at least one further comonomer, such as (meth) acrylic acid C 1 -C 10 -alkyl ester, maleic anhydride, isobutene or vinyl acetate, preferably by copolymerization at temperatures in the range of 190 to 350 ° C and pressures in the range of 1500 to 3500, preferably 2000 to 2500 bar.
• Ethylene (meth) acrylic acid copolymers which are particularly suitable as binders (b) may contain, for example, up to 90% by weight of ethylene in copolymerized form and have a kinematic melt viscosity in the range from 60 mm 2 / s to 10,000 mm 2 / s, preferably 100 mm 2 / s to 5,000 mm 2 / s, measured at 120 ° C.
• Ethylene (meth) acrylic acid copolymers which are particularly suitable as binder (b) may comprise, for example, up to 90% by weight of ethylene in copolymerized form and have a melt flow rate (MFR) in the range from 1 to 50 g / 10 min, preferably 5 to 20 g / 10 min, more preferably 7 to 15 g / 10 min, measured at 160 ° C and a load of 325 g according to EN ISO 1133.
• MFR melt flow rate
• binders (b) are copolymers of at least one vinylaromatic with at least one conjugated diene and optionally further comonomers, for example styrene-butadiene binders, at least one ethylenically unsaturated carboxylic acid or dicarboxylic acid or a suitable derivative, for example the corresponding anhydride, in copolymerized form.
• Particularly suitable vinylaromatics are para-methylstyrene, .alpha.-methylstyrene and in particular styrene.
• Particularly suitable conjugated dienes are isoprene, chloroprene and in particular 1,3-butadiene.
• Particularly suitable ethylenically unsaturated carboxylic acids or dicarboxylic acids or suitable derivatives thereof are exemplified by (meth) acrylic acid, maleic acid, itaconic acid, maleic anhydride or itaconic anhydride.
• binders (b) particularly suitable copolymers of at least one vinylaromatic copolymerized with at least one conjugated diene and optionally further comonomers are copolymerized: from 19.9 to 80% by weight of vinylaromatic, from 19.9 to 80% by weight conjugated diene, 0.1 to 10% by weight of ethylenically unsaturated carboxylic acid or dicarboxylic acid or a suitable derivative, for example the corresponding anhydride.
• binder (b) has a dynamic viscosity at 23 ° C in the range of 10 to 100 dPa ⁇ s, preferably 20 to 30 dPa ⁇ s, determined, for example, by rotational viscometry, for example with a Haake viscometer.
• emulsifier (c) it is possible to use anionic, cationic or preferably nonionic surface-active substances.
• Suitable cationic emulsifiers (c) are, for example, C 6 -C 18 -alkyl-, aralkyl- or heterocyclic radical-containing primary, secondary, tertiary or quaternary ammonium salts, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of Amine oxides, quinolinium salts, isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
• Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklareester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide.
• Suitable anionic emulsifiers (c) are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: from 4 to 30, alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50, alkyl radical: C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ) and of sulfosuccinates, such as, for example, sulfosuccinic mono- or diesters.
• alkyl sulfates alkyl radical: C 8 to C 12
• sulfuric monoesters of ethoxylated alkanols degree of ethoxy
• aryl- or alkyl-substituted polyglycol ethers Preference is given to aryl- or alkyl-substituted polyglycol ethers, furthermore substances which are known in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.
• nonionic emulsifiers (c) such as, for example, mono- or preferably polyalkoxylated C 10 -C 30 -alkanols, preferably with three to one hundred mol of C 2 -C 4 -alkylene oxide, in particular ethylene oxide alkoxylated oxo or fatty alcohols.
• formulations used in step (A), in particular printing formulations may comprise at least one rheology modifier (d) selected from thickeners (d1), which may also be referred to as thickeners, and viscosity-reducing agents (d2).
• rheology modifier selected from thickeners (d1), which may also be referred to as thickeners, and viscosity-reducing agents (d2).
• Suitable thickeners (d1) are, for example, natural thickeners or preferably synthetic thickeners.
• Natural thickeners are those thickeners which are natural products or can be obtained by work-up such as, for example, cleaning operations, in particular extraction of natural products.
• inorganic natural thickeners are phyllosilicates such as bentonite.
• organic natural thickeners are preferably proteins such as casein or preferably polysaccharides.
• Particularly preferred natural thickening agents are selected from agar-agar, carrageenan, gum arabic, alginates such as sodium alginate, potassium alginate, ammonium alginate, calcium alginate and propylene glycol alginate, pectins, polyoses, carob bean gum and dextrins.
• synthetic thickening agents which are selected from generally liquid solutions of synthetic polymers, in particular acrylates, in, for example, white oil or as aqueous solutions, and of synthetic polymers in dried form, for example as a powder prepared by spray-drying.
• Contain as synthetic thickener (d1) used synthetic polymers Acid groups that are completely or to some extent neutralized with ammonia. Ammonia is released during the fixation process, which lowers the pH and starts the fixation process.
• the lowering of the pH necessary for fixation can alternatively be effected by addition of nonvolatile acids such as citric acid, succinic acid, glutaric acid or malic acid.
• Very particularly preferred synthetic thickeners are selected from copolymers of 85 to 95% by weight of acrylic acid, 4 to 14% by weight of acrylamide and 0.01 to at most 1% by weight of the (meth) acrylamide derivative of the formula I. with molecular weights M w in the range of 100,000 to 2,000,000 g / mol, in which the radicals R 1 may be identical or different and may denote methyl or hydrogen.
• thickeners (d1) are selected from reaction products of aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or dodecane-1,12-diisocyanate with preferably 2 equivalents of polyalkoxylated fatty alcohol or oxo alcohol, for example 10 to 150-fold ethoxylated C 10 -C 30 Fatty alcohol or C 11 -C 31 oxo alcohol.
• aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate or dodecane-1,12-diisocyanate with preferably 2 equivalents of polyalkoxylated fatty alcohol or oxo alcohol, for example 10 to 150-fold ethoxylated C 10 -C 30 Fatty alcohol or C 11 -C 31 oxo alcohol.
• Suitable viscosity-lowering agents (d2) are, for example, organic solvents such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethylene glycol, diethylene glycol, butyl glycol, dibutyl glycol, and, for example, residual alcohol-free alkoxylated nC 4 -C 8 -alkanol, preferably residual alcohol-free one to 10-fold, more preferably 3 to 6-fold ethoxylated nC 4 -C 8 -alkanol. In this case, residual alcohol is to be understood as meaning the respective non-alkoxylated nC 4 -C 8 -alkanol.
• organic solvents such as dimethyl sulfoxide (DMSO), N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP), ethylene glycol, diethylene glycol, butyl glycol, dibutyl glycol
• formulation used in step (A) in particular printing formulation in the range from 10 to 90% by weight, preferably from 50 to 85% by weight, particularly preferably from 60 to 80% by weight, of metal powder (a), in the range of 1 to 20% by weight, preferably 2 to 15% by weight of binder (b), in the range from 0.1 to 4% by weight, preferably up to 2% by weight, of emulsifier (c), in the range of 0 to 5% by weight, preferably 0.2 to 1% by weight of rheology modifier (d), wherein in wt .-% in each case on the total in step (A) used formulation or printing formulation are based and where in wt .-% of binder (b) on the solids content of the respective binder (b) relate.
• step (A) of the process according to the invention can be printed with a formulation, in particular printing formulation, in addition to metal powder (a) and optionally binder (b), emulsifier (c) and optionally rheology modifier (d) at least one Aid (s) contains.
• a formulation in particular printing formulation, in addition to metal powder (a) and optionally binder (b), emulsifier (c) and optionally rheology modifier (d) at least one Aid (s) contains.
• Aid s
• auxiliaries (e) mention may be made of handle improvers, defoamers, wetting agents, leveling agents, urea, corrosion inhibitors, active substances such as, for example, biocides or flameproofing agents and crosslinking agents.
• Suitable defoamers are, for example, silicone-containing defoamers such as, for example, those of the formula HO- (CH 2 ) 3 -Si (CH 3 ) [OSi (CH 3 ) 3 ] 2 and HO- (CH 2 ) 3 -Si (CH 3 ) [OSi ( CH 3 ) 3 ] [OSi (CH 3 ) 2 OSi (CH 3 ) 3 ], not alkoxylated or alkoxylated with up to 20 equivalents of alkylene oxide and in particular ethylene oxide.
• Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C 10 -C 20 -alkanols, unbranched C 10 -C 20 -alkanols and 2-ethylhexan-1-ol.
• Further suitable defoamers are fatty acid C 8 -C 20 -alkyl esters, preferably C 10 -C 20 -alkyl stearates, in which C 8 -C 20 -alkyl, preferably C 10 -C 20 -alkyl, may be unbranched or branched.
• suitable wetting agents are nonionic, anionic or cationic surfactants, in particular ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether sulfates, alkylpolyglycosides, alkylphosphonates, alkylphenylphosphonates, Alkyl phosphates, or alkylphenyl phosphates.
• nonionic, anionic or cationic surfactants in particular ethoxylation and / or propoxylation products of fatty alcohols or propylene oxide-ethylene oxide block copolymers, ethoxylated or propoxylated fatty or oxo alcohols, furthermore ethoxylates of oleic acid or alkylphenols, alkylphenol ether s
• Suitable leveling agents are, for example, block copolymers of ethylene oxide and propylene oxide with molecular weights M n in the range from 500 to 5000 g / mol, preferably 800 to 2000 g / mol.
• block copolymers of propylene oxide / ethylene oxide for example of the formula EO 8 PO 7 EO 8 , where EO is ethylene oxide and PO is propylene oxide.
• Suitable biocides are, for example, commercially available as Proxel brands. Examples include: 1,2-Benzisothiazolin-3-one (“BIT”) (commercially available as Proxel® brands from. Avecia Lim.) And its alkali metal salts; other suitable biocides are 2-methyl-2H-isothiazol-3-one (“MIT”) and 5-chloro-2-methyl-2H-isothiazol-3-one (“CIT”).
• BIT 1,2-Benzisothiazolin-3-one
• MIT 2-methyl-2H-isothiazol-3-one
• CIT 5-chloro-2-methyl-2H-isothiazol-3-one
• Suitable crosslinkers are, for example, condensation products of glyoxal, urea, formaldehyde and optionally one or more alcohols, such as C 1 -C 4 -alkanols or ethylene glycol, in particular DMDHEU (N, N'-dihydroxymethylol-4,5-dihydroxymethyleneurea), melamine and condensation products of melamine with aldehydes, in particular formaldehyde, and optionally one or more alcohols, such as C 1 -C 4 -alkanols or ethylene glycol, isocyanurates, in particular cyclic trimers of hexamethylene diisocyanate, and carbodiimides, in particular polymeric carbodiimides.
• alcohols such as C 1 -C 4 -alkanols or ethylene glycol
• DMDHEU N, N'-dihydroxymethylol-4,5-dihydroxymethyleneurea
• formulation used in step (A), in particular printing formulation comprises auxiliaries (e) up to 30% by weight, based on the sum of metal powder (a), binder (b), emulsifier (c) and optionally Rheology modifier (d).
• step (A) such patterns are applied, in particular by printing, in which metal powders (a) are arranged in the form of straight or preferably curved stripe patterns or line patterns on textile, said lines having, for example, a width and Thickness in each case in the range of 0.1 .mu.m to 5 mm and said strips can have a width in the range of 5.1 mm to, for example, 10 cm or optionally more and a thickness of 0.1 .mu.m to 5 mm.
• step (A) such stripe patterns or line patterns of metal powder (a) are applied, in particular by printing, in which the stripes do not touch or intersect.
• step (A) in step (A), a formulation is applied over a flat area.
• step (A) methods are printed which are known per se.
• a stencil is used by means of which the formulation, in particular printing formulation, containing metal powders (a) is pressed with a doctor blade.
• the method described above belongs to the screen printing method.
• Other suitable printing processes are gravure printing and flexographic printing.
• Another suitable printing method is selected from valve jet method. Valve-jet processes use such a printing formulation, which preferably contains no thickening agent (d1).
• a further metal is deposited on the textile surface in step (B). It is in step (B) possible to deposit one or more other metals, preferably only one more metal is deposited.
• a further metal is deposited on the textile surface in step (B).
• the textile surface is meant the textile surfaces which have previously been processed after the steps (A) to (B) and optionally further steps such as (D).
• step (B) It is possible to deposit several further metals in step (B), but it is preferable to deposit only one more metal.
• metal powder (a) in step (A) carbonyl iron powder is selected and, as further metal in step (B), silver, gold or, in particular, copper.
• metal is deposited so much further that a layer thickness in the range from 100 nm to 500 ⁇ m, preferably from 1 ⁇ m to 100 ⁇ m, particularly preferably 2 ⁇ m to 50 ⁇ m, is produced.
• metal powder (a) is in most cases partially or completely replaced by further metal, wherein the morphology of further deposited metal need not be identical to the morphology of metal powder (a).
• metallized textile surfaces are obtained.
• metallized textiles printed with a line or stripe pattern after step (B) have a resistivity in the range of 1 m ⁇ / cm 2 to 1 M ⁇ / cm 2 or in the range of 1 ⁇ / cm to 1 M ⁇ / cm, measured at room temperature and along the respective strips or lines.
• step (C) at least one textile metallized as described above is combined with one or more layers of textile which may likewise be metallised or which may likewise be metallised.
• the combining can be done, for example, by placing one another on top of each other, for example by placing one on top of another.
• At least three layers of textile, metallized or unmetallized can be joined together to form a composite body.
• the bonding can be done over the entire surface or partially, for example punctiform (punctiform) or in the form of seams.
• the bonding can be done for example by sewing, needling, gluing, quilting, laminating, laminating or welding, in each case over the entire surface, partially or even punctiform. It is particularly preferred to be able to laminate a layer of textile with another layer of textile over the entire surface, to glue it in spots, to partially sew it up or quilt it.
• Inventive multilayer materials are suitable as or for the production of protective clothing, which is also the subject of the present invention. Furthermore, the present invention is the use of multilayer materials according to the invention for the production of protective clothing, and further object of the present invention is a process for the production of protective clothing using multilayer materials according to the invention. The manufacturing can be done by packaging.
• Under protective clothing is for example sportswear to understand, for example, vests or gloves for sports fencers or clothing for participants in paintball tournaments, continue to film actors and stuntmen.
• Protective clothing according to the invention is very well suited to protect against blunt bats, stitches and cuts as well as thrown objects.
• Protective clothing according to the invention is easy to manufacture and does not have to be thick, so that it has high wearing comfort even at relatively high temperatures.
• Shock-resistant clothing is also conceivable, such as so-called bullet-proof vests.
• Inventive multilayer materials are suitable as or for the production of mechanically stressed articles, which are also the subject of the present invention. Furthermore, the present invention, the use of multilayer materials according to the invention for the production of mechanically strained objects, and further object of the present invention is a process for the preparation of mechanically stressed articles using multilayer materials according to the invention.
• Mechanically stressed objects can be strained by stitches, rubbing, cutting or pressure, for example.
• the side panels of car seats are mentioned, which are much strained by getting in and out, continue seats including the backrests in public transport, in addition to the Getting in and out can also suffer from a variety of forms of wanton damage.
• Another object of the present invention is a process for the preparation of multilayer materials according to the invention, hereinafter also referred to as inventive production process.
• step (A) Details of the formulations used in step (A) are described above.
• step (A) such patterns are applied, in particular by printing, in which metal powders (a) are arranged on textile in the form of straight or preferably curved stripe patterns or line patterns, said lines having, for example, a width and Thickness in each case in the range of 0.1 .mu.m to 5 mm and said strips can have a width in the range of 5.1 mm to, for example, 10 cm or optionally more and a thickness of 0.1 .mu.m to 5 mm.
• step (A) such stripe patterns or line patterns of metal powder (a) are applied, in particular by printing, in which the stripes do not touch or intersect.
• step (A) at least one formulation is applied flat, i. over the entire surface.
• step (A) methods are printed which are known per se.
• a stencil is used by means of which the formulation, in particular printing formulation containing metal powders (a), is pressed with a doctor blade.
• the method described above belongs to the screen printing method.
• Other suitable printing processes are gravure printing and flexographic printing.
• Another suitable printing method is selected from valve jet method. Valve-jet processes use such a printing formulation, which preferably contains no thickening agent (d1).
• formulation used in the process according to the invention contains up to 30% by weight of auxiliary agent (s), based on the sum of metal powder (a), binder (b), emulsifier (c) and rheology modifier (i.e. ).
• one or more handle enhancers may be added, for example, one or more silicone emulsions.
• one or more binders (b) and finally optionally one or more rheology modifiers (d) can be added and homogenized with further mixing, for example stirring. It usually comes with relatively short stirring times, for example, 5 seconds to 5 minutes, preferably 20 seconds to 1 minute at stirring speeds in the range of 1000 to 3000 U / min.
• the finished formulation according to the invention in particular printing formulation can, if it is to be used as a printing paste, 30 to 70 wt .-% white oil.
• Aqueous synthetic thickeners (d1) preferably contain up to 25% by weight of synthetic polymer suitable as thickener (d1). If it is desired to use thickeners (d1) in aqueous formulations, aqueous ammonia is generally added.
• the use of granular, solid formulations thickener (c) are applicable to produce emissions-free prints.
• step (B1) the procedure is to operate in step (B1) without an external voltage source and that the further metal in step (B1) in the electrochemical series of the elements, in alkaline or preferably in acidic solution, has a more positive normal potential than metal, which is based on metal powder (a), and as hydrogen.
• step (A) and in step (B) thermally treated textile surface with a basic, neutral or preferably acidic preferably aqueous solution of salt of further metal and optionally one or more reducing agents, for example by inserting it in the solution in question.
• step (B1) in the range of 0.5 minutes, up to 12 hours, preferably up to 30 minutes, are treated.
• step (B1) a basic, neutral or preferably acidic solution of further metal salt is treated which has a temperature in the range of 0 to 100 ° C, preferably 10 to 80 ° C.
• copper is selected as a further metal
• aldehydes in particular reducing sugars or formaldehyde
• nickel is selected as a further metal
• alkali hypophosphite in particular NaH 2 PO 2 .2H 2 O
• boranates in particular NaBH 4
• step (B2) the present invention proceeds by operating in step (B2) with external voltage source and that the additional metal in step (B2) in the electrochemical series of the elements in acidic or alkaline solution may have a stronger or weaker positive normal potential than metal, the metal powder (a) is based.
• this can be used as metal powder (a) carbonyl iron powder and choose as another metal nickel, zinc or in particular copper.
• the further metal in step (B2) has a more positive normal potential in the electrochemical series of the elements than hydrogen, and the metal which is based on metal powder (a) is that additional metal is used in analogy to step ( B1) is deposited.
• step (B2) it is possible, for example, to apply a current having a strength in the range from 10 to 100 A, preferably 12 to 50 A.
• step (B2) it is possible to operate, for example, over a period of 1 to 160 hours using an external power source.
• step (B1) and step (B2) are combined by operating first with and without external voltage source and the other metal in step (B) in the electrochemical series of the elements being more positive Normal potential may have as a metal, the metal powder (a) is based.
• auxiliaries are added to the solution of further metal.
• adjuvants include buffers, surfactants, polymers, in particular particulate polymers whose particle diameter is in the range from 10 nm to 10 ⁇ m, defoamers, one or more organic solvents, one or more complexing agents.
• Particularly suitable buffers are acetic acid / acetate buffer.
• Particularly suitable surfactants are selected from cationic, anionic and in particular nonionic surfactants.
• cationic surfactants which may be mentioned are: primary, secondary, tertiary or quaternary ammonium salts containing C 6 -C 18 -alkyl, alkanolammonium salts, pyridinium salts, imidazolinium salts, oxazolinium salts, morpholinium salts, thiazolinium salts and salts of amine oxides, quinolinium salts , Isoquinolinium salts, tropylium salts, sulfonium salts and phosphonium salts.
• Examples include dodecylammonium acetate or the corresponding hydrochloride, the chlorides or acetates of the various 2- (N, N, N-trimethylammonium) ethylparaffinklareester, N-cetylpyridinium chloride, N-Laurylpyridiniumsulfat and N-cetyl-N, N, N-trimethylammonium bromide, N- Dodecyl-N, N, N-trimethylammonium bromide, N, N-distearyl-N, N-dimethylammonium chloride and the gemini surfactant N, N '- (lauryldimethyl) ethylenediamine dibromide.
• Suitable anionic surfactants are alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C 8 to C 12 ), of sulfuric monoesters of ethoxylated alkanols (degree of ethoxylation: 4 to 30, alkyl radical: C 12 -C 18 ) and ethoxylated alkylphenols (degree of ethoxylation: 3 to 50 , Alkyl radical: C 4 -C 12 ), of alkylsulfonic acids (alkyl radical: C 12 -C 18 ), of alkylarylsulfonic acids (alkyl radical: C 9 -C 18 ) and of sulfosuccinates, such as, for example, sulfosuccinic mono- or diesters.
• alkyl sulfates alkyl radical: C 8 to C 12
• sulfuric monoesters of ethoxylated alkanols degree of ethoxylation: 4 to 30, al
• aryl- or alkyl-substituted polyglycol ethers Preference is given to aryl- or alkyl-substituted polyglycol ethers, furthermore substances which are known in US 4,218,218 and homologues with y (from the formulas US 4,218,218 ) in the range of 10 to 37.
• nonionic surfactants such as, for example, mono- or preferably polyalkoxylated C 10 -C 30 alkanols, preferably with three to one hundred moles of C 2 -C 4 -alkylene oxide, in particular ethylene oxide alkoxylated oxo or fatty alcohols.
• Suitable defoamers are, for example, silicone-containing defoamers such as, for example, those of the formula HO- (CH 2 ) 3 -Si (CH 3 ) [OSi (CH 3 ) 3 ] 2 and HO- (CH 2 ) 3 -Si (CH 3 ) [OSi ( CH 3 ) 3 ] [OSi (CH 3 ) 2 OSi (CH 3 ) 3 ], not alkoxylated or alkoxylated with up to 20 equivalents of alkylene oxide and in particular ethylene oxide.
• Silicone-free antifoams are also suitable, for example polyalkoxylated alcohols, for example fatty alcohol alkoxylates, preferably 2 to 50-times ethoxylated preferably unbranched C 10 -C 20 -alkanols, unbranched C 10 -C 20 -alkanols and 2-ethylhexan-1-ol.
• Further suitable defoamers are fatty acid C 8 -C 20 -alkyl esters, preferably C 10 -C 20 -alkyl stearates, in which C 8 -C 20 -alkyl, preferably C 10 -C 20 -alkyl, may be unbranched or branched.
• Suitable complexing agents are those compounds which form chelates. Preference is given to those complexing agents which are selected from amines, diamines and triamines which carry at least one carboxylic acid group. Examples include nitrilotriacetic acid, ethylenediaminetetraacetic acid and Diethylenpentaminpentaessigklare and the corresponding alkali metal salts mentioned.
• step (C) at least one textile metallized as described above is combined with one or more layers of textile which may likewise be metallised or which may likewise be metallised.
• the combining can be done, for example, by placing one another on top of each other, for example by placing one on top of another.
• At least three layers of textile, metallized or unmetallized can be joined together to form a composite body.
• the bonding can be done over the entire surface or partially, for example punctiform (punctiform) or in the form of seams.
• the bonding can be done for example by sewing, needling, gluing, quilting, laminating, laminating or welding, in each case over the entire surface, partially or even punctiform. It is particularly preferred to be able to laminate a layer of textile with another layer of textile over the entire surface, to glue it in spots, to partially sew it up or quilt it.
• one or more thermal treatment steps (D) may be performed following step (A) or step (B).
• thermal treatment steps carried out immediately after step (A) are also referred to as thermal treatment steps (D1) and thermal treatment steps carried out immediately after step (B) also take the form of thermal treatment steps (D2).
• thermal treatment steps If one wishes to carry out several thermal treatment steps, one can carry out the various thermal treatment steps at the same or preferably at different temperatures.
• step (D) or each individual step (D) can be treated, for example, at temperatures in the range of 50 to 200 ° C. Care must be taken to ensure that the thermal treatment according to step (D) does not allow the material from which the textile surface used as starting material softens or even melts. It remains in any case with the temperature below the softening or melting point of the textile material in question, or one chooses the duration of the thermal treatment so short that a softening or even melting does not take place.
• step (D) or each individual step (D) can be treated, for example, over a period of 10 seconds to 15 minutes, preferably 30 seconds to 10 minutes.
• a first step (D1) at temperatures in the range of, for example, 50 to 110 ° C over a period of 30 seconds to 3 minutes and in a second step (D2) then at temperatures in the range of 130 ° C to 200 ° C over a period of 30 seconds to 15 minutes.
• step (D) or each individual step (D) in devices known per se, for example in drying cabinets, tenter frames or vacuum drying cabinets.
• corrosion-inhibiting layers are layers of one or more of the following materials: waxes, in particular polyethylene waxes, lacquers, for example aqueous base lacquers, 1,2,3-benzotriazole and salts, in particular sulfates and methosulfates of quaternized fatty amines, for example lauryl / myristyltrimethylammonium methosulfate ,
• films for example, films, in particular polymer films, for example of polyester, polyvinyl chloride, thermoplastic polyurethane (TPU) or in particular polyolefins such as polyethylene or polypropylene, where polyethylene and polypropylene in each case also copolymers of ethylene or propylene are to be understood.
• TPU thermoplastic polyurethane
• polyolefins such as polyethylene or polypropylene, where polyethylene and polypropylene in each case also copolymers of ethylene or propylene are to be understood.
• a flexible layer is a binder (b2) which may be the same or different from optionally printed binder (b1) from step (A).
• step (F) If a binder has been applied in step (F), it is then possible to re-treat it thermally according to step (D).
• the mixture was stirred at 5000 rpm for a period of 20 minutes (Ultra-Thurrax).
• polyester paste I printed on one side over the entire surface of a polyester fleece, basis weight 90 g / m 2 - with a sieve, mesh 80th
• step (B) without external power source
• polyester fleece was removed, rinsed twice under running water and dried at 90 ° C. over a period of one hour.
• Example III Two identically cut pieces of a metallised textile from Example III were taken. On the metallized side was applied by screen printing in a punctiform pattern, a commercial adhesive formulation consisting of an isocyanate group-containing polymer. These fabrics were then transferred to both sides of a third, non-metallized textile (polyester non-woven, basis weight 90 g / m 2) is placed, so that the printed adhesive side showed for the third fabric respectively, and pressed at 80 ° C under pressure for one minute. The result was a novel multilayer material that was designed as a flexible composite, consisting of two layers of metallized textile and a layer of non-metallized textile.
• the multilayer system according to the invention is extremely stable against scrubbing and against punctures with a sharp kitchen knife. Even after punctiform damage, the mechanical stability does not diminish significantly.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Ceramic Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Laminated Bodies (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Seats For Vehicles (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2007
  • 2007-12-06 DE DE102007055725A patent/DE102007055725A1/de not_active Withdrawn
• 2008
  • 2008-12-02 JP JP2010536426A patent/JP2011506126A/ja not_active Withdrawn
  • 2008-12-02 US US12/744,004 patent/US20100263109A1/en not_active Abandoned
  • 2008-12-02 CA CA2705491A patent/CA2705491A1/en not_active Abandoned
  • 2008-12-02 WO PCT/EP2008/066639 patent/WO2009071547A1/de active Application Filing
  • 2008-12-02 RU RU2010127422/05A patent/RU2010127422A/ru not_active Application Discontinuation
  • 2008-12-02 EP EP08856595.7A patent/EP2220287B1/de not_active Not-in-force

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