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
  • D06M17/00—Producing multi-layer textile fabrics
• • 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
  • D06M17/00—Producing multi-layer textile fabrics
  • D06M17/04—Producing multi-layer textile fabrics by applying synthetic resins as adhesives
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N7/00—Flexible sheet materials not otherwise provided for, e.g. textile threads, filaments, yarns or tow, glued on macromolecular material
  • D06N7/0092—Non-continuous polymer coating on the fibrous substrate, e.g. plastic dots on fabrics
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2205/00—Condition, form or state of the materials
  • D06N2205/02—Dispersion
  • D06N2205/023—Emulsion, aqueous dispersion, latex

Definitions

• the invention relates to the use of a protective colloid-stabilized polymer for Coating of a carrier material.
• a sub-item is first printed on the material to be coated. This printing can be done by rotary screen printing.
• the sub-item is a paste containing an aqueous dispersion of an emulsifier-stabilized polymer, thickener and optionally pressure assistants.
• Hot melt glue spread Excess powder is sucked off. After that, the Subpoint with the hot melt adhesive powder first dried and sintered, or Hot melt adhesive is melted.
• a coated sheet comprising a coating carrier (present also referred to as a carrier material), a base or base layer applied thereon a plastic compound (also referred to herein as sub-item) and one on it provided second layer (also referred to herein as hot melt adhesive) comprises.
• the Base layer is composed of a crosslinkable, aqueous polymer dispersion, emulsion and / or solution produced.
• polymer dispersions self-crosslinking acrylic polymers, self-crosslinking polyvinyl esters or self-crosslinking styrene-acrylic or acrylic-vinyl ester copolymers used.
• the polymers used preferably have one Film formation temperature of at least 5 ° C and are usually in dispersion or emulsion form sour.
• the present invention is therefore based on the object to overcome these disadvantages.
• a protective colloid-stabilized polymer comprising a protective colloid and a polymer, dissolved for coating a support material.
• Emulsifiers are compounds which can be subsumed under the term "surfactants".
• Surfactants are compounds which can be subsumed under the term "surfactants".
• Protective colloids are surface-active substances, but they have very characteristic differences to surfactants.
• a characteristic feature of surfactants and their solutions is micelle formation. As the surfactant concentration increases, the number of molecules increases at the interface until there is no room for more. Then the time for the formation of micelles is given.
• the formation of micelles starts in a narrow range of concentration characteristic of each surfactant and depends on the molecular structure. It occurs at the concentration at which the surface is completely or substantially fully occupied and therefore the surface tension becomes independent of the increase in the concentration. By measuring the surface tension as a function of the concentration, the concentration at which the micelle formation begins can be determined in a simple manner. It is called the critical micelle concentration (CMC).
• CMC critical micelle concentration
• HLB value hydrophilic-lipophilic balance
• Protective colloid-stabilized polymers are known to the person skilled in the art. They are commercial or can be obtained by free-radically initiated polymerization of monomers below and optionally Hilfsmonomere be prepared.
• the free-radical polymerization of ethylenic unsaturated monomers can be made by suspension or emulsion polymerization. In the suspension and emulsion polymerization, in the presence of surface-active Substances of composition of 100-51% protective colloids and 0-49% emulsifiers polymerized.
• Suitable emulsifiers are both anionic, cationic and nonionic emulsifiers, for example anionic surfactants, such as alkyl sulfates having a Chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in hydrophobic group and up to 60 ethylene or propylene oxide units, alkyl or Alkylarylsulfonate with 8 to 18 C-atoms, esters and half esters of sulfosuccinic acid with monohydric alcohols or alkylphenols, or nonionic surfactants such as alkyl polyglycol ethers or alkylaryl polyglycol ethers having up to 60 ethylene oxide or propylene oxide units.
• anionic surfactants such as alkyl sulfates having a Chain length of 8 to 18 carbon atoms, alkyl or alkylaryl ether sulfates having 8 to 18 carbon atoms in hydropho
• protective colloids are modified natural polymers, such as O-methylcellulose, O- (2-hydroxy-ethyl) -cellulose, O- (2-hydroxy-propyl) -cellulose, O- (2-hydroxy-propyl) -O-methyl-cellulose, O- (2-hydroxybutyl) -O-methyl-cellulose, carboxymethylcellulose (Na salt), starch ether, O- (2-hydroxypropyl) starch and lignosulfonic acid, synthetic homopolymers and copolymers, such as poly (vinyl alcohol) [partially saponified poly (vinyl acetate)], Poly (vinyl alcohol-co-ethylene), poly (methacrylic acid-sodium salts), poly [methacrylic acid-sodium-salt-co- (methacrylic acid-methyl ester)], Poly [acrylic acid-co-acrylic acid (2-ethyl-hexyl)], Poly [methacrylic acid (hydroxyl-alkyl ester)], poly (styl alcohol
• the polymers of the protective colloid-stabilized polymer are described below with reference to Monomers explained in more detail.
• the monomers may be ethylenic unsaturated monomers act.
• vinyl esters of unbranched or branched alkylcarboxylic acids having 1 to 18 carbon atoms acrylic acid esters or methacrylic acid esters of branched or unbranched alcohols or diols with 1 to 18 C atoms
• C2-C20 mono- or di-carboxylic acids their amides, N-methylolamides or Nitriles
• C2-C20 sulfonic acids 3-20-membered heterocyclic compounds with oxygen, Sulfur, selenium, tellurium, nitrogen, phosphorus, boron or aluminum as heteroatom
• dienes with at least 4 C atoms olefins having at least 2 C atoms
• vinyl aromatics in particular with Benzene or naphthalene as aromatic and C2-C20 vinyl halides.
• Preferred vinyl esters are those having 1 to 12 C atoms, in particular vinyl acetate, Vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methyl vinyl acetate, vinyl pivalate and vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 13 C atoms.
• the acrylic or methacrylic acid ester an ester of unbranched or branched alcohols having 1 to 15 carbon atoms, in particular Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate and 2-ethylhexyl acrylate, especially methyl acrylate, methyl methacrylate, n-butyl acrylate, t-butyl acrylate, t-butyl acrylate and 2-ethylhexyl acrylate.
• Preferred mono- and di-carboxylic acids their amides, N-methylol amides and nitriles selected from acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide, N-methylolacrylamide, N-methylolmethacrylamide and acrylonitrile.
• the sulfonic acid is conveniently vinylsulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid selected.
• the preferred heterocyclic compounds are Vinyl pyrrolidone and vinyl pyridine.
• the vinyl aromatic is styrene, methyl styrene or vinyl toluene.
• the vinyl halide is vinyl chloride.
• the olefin selected from ethylene and propylene.
• Preferred dienes are selected from 1,3-butadiene and isoprene.
• auxiliary monomers are ethylenically unsaturated C2-C20 mono- and dicarboxylic acids, preferably acrylic acid, methacrylic acid, fumaric acid and maleic acid; ethylenically unsaturated C 2 -C 20 -carboxylic acid amides and nitriles, preferably acrylamide and acrylonitrile; Mono- and diesters of fumaric acid and maleic acid such as the diethyl and diisopropyl esters, as well as maleic anhydride, ethylenically unsaturated C 2 -C 20 -sulfonic acids or their salts (alkali, alkaline earth and ammonium salts), preferably Vinylsulfonic acid, 2-acrylamido-2-
• precrosslinking C2-C20 comonomers such as polyethylenically unsaturated comonomers, For example, divinyl adipate, diallyl maleate, diallyl phthalate, allyl methacrylate or Triallyl cyanurate, or post-crosslinking comonomers, for example Acrlyamidoglykolklare (AGA), Methylacrylamidoglycolic acid methyl ester (MAGME), N-methylolacrylamide (NMA), N-methylolmethacrylamide, N-methylolallyl carbamate, C2-C20 alkyl ethers, such as the isobutoxy ether or esters of N-methylolacrylamide, N-methylolmethacrlyamide and N-methylolallylcarbamate.
• AGA Acrlyamidoglykolklad by Methylacrylamidoglycolic acid methyl ester
• NMA Methylacrylamidoglycolic acid methyl ester
• epoxide-functional C2-C20 comonomers such as Glycidyl methacrylate and glycidyl acrylate.
• silicon-functional C2-C20 comonomers such as acryloxypropyltri (alkoxy) and methacryloxypropyltri (alkoxy) silanes, Vinyltrialkoxysilane and Vinylmethyldialkoxysilane, wherein as alkoxy groups, for example Ethoxy and Ethoxypropylenglykolether residues may be included.
• C2-C20 monomers with hydroxy or CO groups for example methacrylic acid and Acrylic acid hydroxyalkyl esters, such as hydroxyethyl, hydroxypropyl or hydroxybutyl acrylate or methacrylate and compounds such as diacetoneacrylamide and acetylacetoxyethyl acrylate or methacrylate.
• the polymers are prepared from monomers or mixtures which one or more monomers from the group vinyl acetate, vinyl esters of ⁇ -branched Monocarboxylic acids having 9 to 13 C atoms, vinyl chloride, ethylene, methyl acrylate, Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate or styrene.
• mixtures of vinyl acetate with ethylene of vinyl acetate, ethylene and a Vinyl esters of ⁇ -branched monocarboxylic acids having 9 to 13 carbon atoms; of n-butyl acrylate, 2-ethylhexyl acrylate and / or methyl methacrylate; of styrene with one or more monomers from the group of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; of vinyl acetate with one or more monomers from the group of methyl acrylate, Ethyl acrylate, propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate and optionally ethylene; wherein said mixtures optionally still one or more of the above May contain auxiliary monomers.
• These mixtures have proven to be particularly favorable because they show excellent properties in coatings at low cost.
• the monomer selection or the selection of the proportions by weight of the comonomers can be so be carried out that in general a glass transition temperature Tg of -50 ° C to + 120 ° C, preferably -30 ° C to + 95 ° C results.
• the glass transition temperature Tg of the polymer can be determined in a known manner by means of differential scanning calorimetry (DSC).
• Tgn Glass transition temperature in Kelvin of the homopolymer of the monomer n.
• Tg values for Homopolymers are described in Polymer Handbook 2nd Edition, J. Wiley & Sons, New York (1975) listed.
• the polymerization of the above monomers and optionally auxiliary monomers to the polymer can be radically intiiert.
• the radically initiated polymerization of the ethylenically unsaturated Monomers can be made by suspension polymerization and emulsion polymerization.
• the polymerization temperature may be 40 ° C to 100 ° C, preferably 60 ° C to 90 ° C.
• gaseous comonomers such as ethylene, 1,3-butadiene or Vinyl chloride
• initiation of the polymerization can be carried out with the customary water-soluble or monomer-soluble initiators or redox initiator combinations take place.
• water-soluble initiators examples include the sodium, potassium and ammonium salts of Peroxodisulfuric acid, hydrogen peroxide, t-butyl peroxide, potassium peroxodiphosphate, t-butyl peroxopivalate, Cumene hydroperoxide, isopropylbenzene monohydroperoxide, azobisisobutyronitrile.
• Examples of monomer-soluble initiators are dicetyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, Dibenzoyl peroxide, tert-butyl peroxyneodecanoate, tert-butyl peroxy-2-ethylhexanoate and tert-butyl peroxypivalate.
• the mentioned initiators are in the In general, in an amount of 0.01 to 10.0 wt .-%, preferably 0.1 to 0.5 wt .-%, respectively based on the total weight of the monomers, used as redox initiators Combinations of the mentioned initiators can be used with reducing agents.
• Suitable reducing agents are the sulfites and bisulfites of the alkali metals and of ammonium, For example, sodium sulfite, the derivatives of sulfoxylic acid, such as zinc or Alkali metal formaldehyde sulfoxylates, for example sodium hydroxymethanesulfinate, and ascorbic acid.
• the amount of reducing agent is generally from 0.01 to 10.0 wt .-%, preferably 0.1 to 0.5 wt .-%, each based on the total weight of the monomers.
• the monomers can be submitted in total, be metered in total or in Shares are submitted and added the remainder after the initiation of the polymerization become.
• the dosages can be carried out separately (spatially and temporally) or the All or part of the components to be dosed can be added pre-emulsified.
• suspension and emulsion polymerization can be polymerized in the presence of the aforementioned protective colloids to the produce protective colloid-stabilized polymers.
• the present invention in particular in the above-described preferred Embodiments has a number of advantages: First, it has been found that very low compared to other prior art coating methods Coating quantities are sufficient for sufficiently good adhesion. This is one To achieve a significant reduction in costs, and exhibit the bonded textile materials a pleasant soft grip on. With the invention used Protective colloid-stabilized polymers is a very high adhesion of the bonded textiles determine. The connection of the scattering powder to the sub-point is very good. The Adhesions associated with the coating using a protective colloid stabilized polymer are very good wash and cleaning resistant.
• the protective colloid-stabilized Polymers are used in the form of a paste.
• Paste is made from a dispersion of the protective colloid-stabilized polymer in water went out.
• the amount of water for example, about 70 wt .-%, based to the dispersion, and that of the protective colloid stabilized polymer about 30 wt .-%, also based on the dispersion amount.
• These polymer dispersions can then thickener and optionally printing assistant may be added, which then paste for coating to be obtained.
• These pastes can, for example in rotary screen printing on the coated Carrier material can be applied. In this way, a sub item for the Colon coating are produced. At the subpoint can then Melted hot melt powder are sprinkled. Excess powder can subsequently be sucked off become. The sub-item can then be dried and sintered, or the scattering powder be melted.
• the above-mentioned polymer dispersions have the advantage that they can be obtained by adding Compounds containing 2 or more epoxide, organo, halogen, hydroxy, aziridine, carbodiimide, Oxazoline, alcohol, amine, aminosilane, aminoformaldehyde, isocyanate or N-2-hydroxyalkylamide residues can be networked.
• Compounds containing 2 or more epoxide, organo, halogen, hydroxy, aziridine, carbodiimide, Oxazoline, alcohol, amine, aminosilane, aminoformaldehyde, isocyanate or N-2-hydroxyalkylamide residues can be networked.
• the intramolecular crosslinking of the Polymer also occurs a crosslinking of the polymer with the Schutzkolloidhülle and with the added additives. As a result, particularly high adhesive strengths are achieved.
• crosslinkers for example, compounds having two or more epoxy, organo, halogen, hydroxy, Aziridine, carbodiimide, oxazoline, alcohol, amine, aminosilane, aminoformaldehyde, isocyanate or N-2-hydroxyalkylamide residues.
• the substrates that can be coated may be materials to act of any kind. It can be flexible, not very flexible or not flexible at all. examples are textile materials of any kind, such as woven, knitted, woven knitted fabric, Raschelwaren (natural and synthetic fibers), fleece of any material. Furthermore, films can be coated be made, in particular of plastics of any kind, as well as paper, artificial leather, leather, Synthetic leather, foam and wood.

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• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
• Paints Or Removers (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (10)

• 2003
  • 2003-12-12 DE DE50302798T patent/DE50302798D1/de not_active Expired - Fee Related
  • 2003-12-12 ES ES03028481T patent/ES2259747T3/es not_active Expired - Lifetime
  • 2003-12-12 EP EP03028481A patent/EP1541751B1/fr not_active Expired - Lifetime
  • 2003-12-12 AT AT03028481T patent/ATE321909T1/de not_active IP Right Cessation
• 2004
  • 2004-12-01 WO PCT/EP2004/013642 patent/WO2005059238A1/fr active Application Filing
  • 2004-12-01 US US10/582,072 patent/US20070128362A1/en not_active Abandoned
  • 2004-12-01 KR KR1020067011386A patent/KR20060121165A/ko not_active Application Discontinuation

Patent Citations (10)

Non-Patent Citations (1)

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