Classifications

• • 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
• • 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
• • 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
  • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
  • D06N3/0031—Retractable fibres; Shrinking of fibres during manufacture
• • 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
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
  • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
• • 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
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
  • Y10T428/24438—Artificial wood or leather grain surface

Definitions

• This invention relates to grained, textile flat materials coated with polyurethane (PU) compositions and to a process for the production thereof and to decorative starting materials comprising such flat materials.
• PU polyurethane
• coated textile flat materials for example for the production of artificial leather.
• the coating composition is applied onto the substrate in single or multiple layers in the direct coating process or using the transfer process.
• the coated textile flat materials may be used, for example, for the production of outer clothing, material for shoe uppers and linings, material for purses and similar articles, material for upholstery and for automotive interior trim.
• a predetermined pattern is embossed onto a coated support material by the action of heat and pressure on embossing calendars, embossing plates or also transfer papers.
• This embossing creates a grain which, however, gives rise to unwanted hardening as a result of the localized compaction.
• This relatively elaborate process is only performed using thermoplastic PU solutions, which sometimes still contain solvent residues which are vaporized by the action of heat.
• Uncontrolled grain patterns may be achieved by treating materials which have been coated using two component PU solutions, if these materials are treated for a certain time using temperatures of for example 20 to 100° C. in an axial centrifugal dryer with an alternating direction of running (for example DE-A 1 760 260). Disadvantages of this process are not only the use of organic solvents, but also the necessity of precise timing of the process steps, which means that the grain must be formed before the system has actually crosslinked.
• embossed surfaces are produced by using grained release materials, in particular release papers or silicone molds.
• the embossed patterns produced with release papers are, however, relatively flat and must be predetermined as early as during the actual coating operation.
• Using silicone molds is highly cost-intensive and only acceptable for special effects.
• An object of the present invention was to provide a process for the production of a deep grain profile on textile flat materials, which process does not exhibit the above-stated disadvantages, and thereby to obtain high quality products by a simple process.
• coated flat materials comprising a grain are obtained if textile flat materials having residual shrinkage are first coated by the direct or reversal process with PU dispersions or solutions and are then subjected to heat treatment.
• the invention relates to a process for the production of grained flat materials comprising coating a textile flat material, which has residual shrinkage, with a polyurethane (PU) dispersion or solution and then post-treating the textile flat material under the influence of heat.
• PU polyurethane
• the invention also relates to a grained, coated textile flat material obtained by using the process according to the invention.
• Textile flat materials for the purposes of the present invention include, for example, woven and knitted fabrics, bonded and unbonded nonwovens and microfibre nonwovens. These may be made from synthetic, natural fibres and/or blends thereof. In principle, in addition to textiles, any other flexible flat materials are suitable for the process according to the invention, provided that they have residual shrinkage.
• Reactive or post-crosslinking PU dispersions are in particular suitable for pretreating the flat materials by coagulation.
• the PU dispersion consisting of blocked isocyanate groups and at least one polyamine, is precipitated by thermal treatment to form a stable, partially crosslinked polyurethane or gel.
• Coagulation is particularly suitable for producing films, for coating the most varied materials and for partially or completely impregnating nonwovens, knitted fabrics or other flat materials for the purpose of stabilization.
• the reactive, post-crosslinkable PU dispersions are applied, for example, by flooding, spraying, dipping, spray application, slop-padding, with a doctor knife or roll or by padding, wherein the dispersions may be used in liquid or foamed form.
• the coating is generally coagulated by dipping in water at a temperature of 50° C. to 120° C., preferably of 75° C. to 98° C. or with hot steam or in an oven by means of radiant heat or high frequency dryers. It is then usually dried at 60° C. to 180° C., preferably at 10° C. to 140° C. and condensation is performed at 140° C. to 165° C.
• the flat materials are held in a stenter frame during crosslinking and drying in order to avoid premature shrinkage of the flat material.
• the resultant coagulate is so resistant, that the precipitation operation after the application can be performed even in the saponification and splitting bath (3% NaOH).
• the polyester content may simultaneously be saponified and dissolved out in that bath. This results in particularly soft flat materials with a pleasant handle.
• coated or filled flat materials may also subsequently be sanded and, in this case, are particularly soft. Mechanical treatment in a tumbling machine also increases softness.
• Electrolyte coagulation proceeds by immersing the coated substrate into a concentrated salt solution or into water combined with acid or the like, wherein the binder coagulates due to the elevated electrolyte content.
• non-post-crosslinkable binders with a heat-sensitive formulation are able to coagulate due to an increase in temperature.
• the precleaned and optionally stabilized textile flat materials are then coated in known manner with the polyurethane systems by the direct or reversal process.
• Coating compositions suitable for the process according to the invention are, for example, both single component and two-component polyurethane systems known in the textiles and leather industry which consist of isocyanate prepolymers and crosslinking agents. They are commercially available as solutions.
• aqueous single component polyurethane dispersions described in DE-A 4 236 569 which additionally contain hydrophilic structures, are suitable coating compositions for the process according to the invention.
• Solvent-free, two-component polyurethane systems consisting of a blocked isocyanate prepolymer and polyamine, which are described for example in EP-A 0 784 097, are particularly suitable. These systems have good wet adhesion and excellent water-resistance. Mixtures of various PU systems are also suitable.
• Coating compositions based on PU dispersions are suitable for the purpose of increasing the wearability of the coated flat materials, as the coatings produced with these PU dispersions are permeable to water vapour.
• the PU coatings are applied onto the substrate by direct spreading using doctor knives, rolls or doctor wires.
• two or more, but preferably two, coats are applied in succession, such that the total thickness of the coating comprising base and topcoat layer(s) is 10 to 100 ⁇ m, preferably 20 to 60 ⁇ m.
• a paste which dries to yield a microporous layer, as described in DE-A 2 020 153, may also be used as the base coat.
• the subsequently applied topcoat protects the overall structure from mechanical stresses and abrasion.
• the coating structure comprising base coat and topcoat may, however, also be applied by the so-called reversal process.
• the reversal process is advantageous when highly flexible substrates, such as knitted fabrics, nonwovens or other non-continuous flat materials, are used.
• the topcoat is initially applied by doctor knife onto a grained or also ungrained transfer paper and dried.
• a preferably foamed intermediate coat is then optionally applied.
• the substrate is gently pressed into the still wet layer.
• a solid composite comprising coating and substrate is obtained, which is removed from the release support and the structure of which largely corresponds to that of the above-described direct coating.
• crosslinking a coated and, depending upon the transfer paper, optionally superficially grained article is obtained.
• the coated flat material may be stored in this form and subsequently subjected to a post-treatment, during which the desired grain and colour may be imparted to the article.
• a grain pattern may be achieved by simply pre-embossing the flat material coated according to the invention, as, under the action of heat in the post-treatment, a matching, but substantially deeper grain forms in the indentations arising from the pre-embossing. Without this pre-embossing, post-treatment yields a somewhat randomly grained product.
• the flat materials coated by the direct process may optionally be subjected to a gentle pre-embossing by means of embossing or goffering calenders.
• pre-embossing to form the grain may be produced by a grained transfer paper.
• untextured release papers or simple dull-finish calendars are used, a random grain is obtained on post-treatment.
• Post-treatment of the coated textile flat materials comprises a subsequent dyeing process or a tensionless treatment with boiling water.
• a subsequent dyeing process or a tensionless treatment with boiling water.
• suitable pigments directly to the coating compositions.
• the coating and support material are coloured using acid dyes, disperse dyes or metal complex dyes depending upon the composition of the base material.
• Metal complex dyes applied direct or also as a lacquer formulation yield the best wet fastness values of the PU coating.
• the flat materials according to the invention may be used as a decorative starting material, for example as an outer clothing material, material for shoe uppers and linings, material for purses and similar articles, material for upholstery and for automotive interior trim.
• the solids content of the dispersion formulation was 4 to 8%.
• the textile flat article was padded with the dispersion formulation (100% liquor absorption) and then coagulated in a steamer at 98° C.
• the nonwoven for example, polyester and polyamide fiber blends
• the nonwoven was treated with splitting during or after completion of coagulation in order to achieve a softer product handle.
• the nonwoven was treated, for example, for approx. 1 hour in 3% sodium hydroxide solution at boiling point, wherein the polyester content was dissolved out.
• the textile was padded with the dispersion formulation (100% liquor absorption) and then dried on a stenter frame.
• Topcoat 650 parts by weight of Impranil ® DLN dispersion (aqueous polyester-polyurethane dispersion) (Bayer AG, Leverkusen) 350 parts by weight of Impranil ® DLF dispersion (Bayer AG, Leverkusen) thickened with Mirox ® AM (Stockhausen, Krefeld) in the presence of ammonia.
• Impranil ® DLN dispersion polyurethane mixture
• Impranil ® DLN dispersion polyurethane mixture
• Impranil ® VP LS 2333 Bayer AG, Leverkusen
• Imprafix ® VP LS Bayer AG, Leverkusen
• isopropanol 1:1
• Stockal ® STA Stockhausen, Krefeld
• Stockal ® SR Stockal ® SR (Stockhausen, Krefeld) are mechanically foamed to 500 g/L and thick- ened with Mirox ® AM (Stockhausen, Krefeld) in the presence of ammonia.
• Adhesion coat 1000 parts by weight of Impranil ® VP LS 2333 (Bayer AG, Leverkusen) 15 parts by weight of Imprafix ® VP LS 2330 (Bayer AG, Leverkusen)/isopropanol (1:1) are thickened with Mirox ® AM (Stockhausen, Krefeld) in the presence of ammonia.
• Polyurethane was generally dyed with metal complex dyes (for example complexing azo dyes, porphyrins or phthalocyanines) and selected acid and disperse dyes (for example azo, triarylmethane or anthraquinone dyes).
• metal complex dyes for example complexing azo dyes, porphyrins or phthalocyanines
• selected acid and disperse dyes for example azo, triarylmethane or anthraquinone dyes
• Dyes used Telon ® monosulfonic acid dye dyes (Dystar, Leverkusen) Isolan S ® 1:2 metal complex dyes dyes (Dystar, Leverkusen) Liquor ratio: 1:40 deionized water Dye 2 to 4% of fabric weight concen- tration: Temperature 40° C. 30 min 100° C. 60 min 100° C. profile during dyeing:

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• 2000
  • 2000-08-11 DE DE10039249A patent/DE10039249A1/de not_active Withdrawn
• 2001
  • 2001-07-30 JP JP2002519715A patent/JP2004506817A/ja active Pending
  • 2001-07-30 MX MXPA03001244A patent/MXPA03001244A/es not_active Application Discontinuation
  • 2001-07-30 CZ CZ2003404A patent/CZ2003404A3/cs unknown
  • 2001-07-30 WO PCT/EP2001/008790 patent/WO2002014596A1/de not_active Application Discontinuation
  • 2001-07-30 AU AU2001279791A patent/AU2001279791A1/en not_active Abandoned
  • 2001-07-30 CA CA002418841A patent/CA2418841A1/en not_active Abandoned
  • 2001-07-30 CN CN01814011A patent/CN1446281A/zh active Pending
  • 2001-07-30 IL IL15414501A patent/IL154145A0/xx unknown
  • 2001-07-30 HU HU0303752A patent/HUP0303752A2/hu unknown
  • 2001-07-30 KR KR10-2003-7001906A patent/KR20030029817A/ko not_active Application Discontinuation
  • 2001-07-30 PL PL35985101A patent/PL359851A1/xx not_active Application Discontinuation
  • 2001-07-30 EP EP01958034A patent/EP1311720A1/de not_active Withdrawn
  • 2001-07-30 BR BR0113172-9A patent/BR0113172A/pt not_active Application Discontinuation
  • 2001-08-09 US US09/925,661 patent/US20020114925A1/en not_active Abandoned

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