EP0165345B1 - Narbenkunstleder mit einer guten Farbechtheit und Verfahren zum Färben von ultrafeinen Polyamidfasern - Google Patents

Narbenkunstleder mit einer guten Farbechtheit und Verfahren zum Färben von ultrafeinen Polyamidfasern Download PDF

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Publication number
EP0165345B1
EP0165345B1 EP19840304074 EP84304074A EP0165345B1 EP 0165345 B1 EP0165345 B1 EP 0165345B1 EP 19840304074 EP19840304074 EP 19840304074 EP 84304074 A EP84304074 A EP 84304074A EP 0165345 B1 EP0165345 B1 EP 0165345B1
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EP
European Patent Office
Prior art keywords
fibers
fiber
ultrafine
artificial leather
polyurethane
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP19840304074
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English (en)
French (fr)
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EP0165345A1 (de
Inventor
Toshio Nishikawa
Shio Imai
Kenkichi Yagi
Yuriko Yoshida
Masato Shimada
Junnosuke Nagashima
Teruo Nakamura
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Toray Industries Inc
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Toray Industries Inc
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Priority to DE8484304074T priority Critical patent/DE3479524D1/de
Publication of EP0165345A1 publication Critical patent/EP0165345A1/de
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Publication of EP0165345B1 publication Critical patent/EP0165345B1/de
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/241—Polyamides; Polyurethanes using acid dyes
    • 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
    • D06N3/0004—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 ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • 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
    • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
    • D06N3/0065—Organic pigments, e.g. dyes, brighteners
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/24—Polyamides; Polyurethanes
    • D06P3/248—Polyamides; Polyurethanes using reactive dyes

Definitions

  • the present invention relates to a grained artificial leather having good colour fastness and to a process for dyeing ultrafine polyamide fibers into deep, bright colours, keeping good colour fastness to dry cleaning in charged system.
  • the grain layer of conventional artificial leathers are made by providing a porous or/and nonporous layer of a resin such as polyurethane on porous sheets made of elastomeric polymers and a fiber base such as woven, non-woven or knitted fabrics.
  • a resin such as polyurethane
  • porous sheets made of elastomeric polymers and a fiber base such as woven, non-woven or knitted fabrics.
  • fiber base such as woven, non-woven or knitted fabrics.
  • such resins do not show good dyeability and colour fastness, especially when subjected to dry cleaning processes.
  • dope dyeing has been applied to the resins of grained surface.
  • dope dyeing is not suitable for manufacturing small quantities of artificial leathers of many colours.
  • the appearance of artificial leathers which are dope dyed is monotonous and opaque due to lack of transparency and lusters.
  • Japanese Patent Publication No. 28041/1973 teaches that some kinds of polyurethane whose soft segment is polyethyleneglycol (PEG-type PU) can be dyed with a metal complex dye.
  • PEG-type PU polyethyleneglycol
  • artificial leathers comprising PEG-type PU and a fiber base of ultra-fine fibers have no great practical value because they do not have good colour fastness as a whole, owing to an insufficient colour fastness of the ultra-fine fibers.
  • the porous resins exhibit poor colour fastness when exposed to dry cleaning and spoil the appearance, not only of the back surface but also, of the grain surface of the artificial leather. The faded porous polyurethane effect even appears through the dyed grained surface.
  • polyamide fibers such as nylon-6 and nylon-66 have such advantages over polyester fibers as softness, high wear resistance and brightness of colour
  • the use of polyamide ultrafine fibers for clothing has been delayed so far because dyes are very liable to come off in washing and dry cleaning.
  • Japanese Patent Publication No. 8128/1981 mentions the attempts to improve colour fastness by increasing molecular orientation of the ultrafine nylon fibers. However their colour fastness is insufficient when exposed to dry cleaning in which charge soap is used. Extra-ultrafine fibers around or less than 0.01 (about 1.11 x 1 0-3 tex) denier always show complete fading of colour even if they are dyed with the dyes said to give highest colour fastness to fibers of ordinary thickness.
  • vat dyes can be also applied to the composite sheet of ultrafine polyamide fiber and polyurethane (Laid-Open Japanese Patent Application Publication No. 1365/1980), they can neither give any heavy sheds nor show good resistance to the synthetic solvents used in dry cleaning. Further, not only do they cause photo- tendering for some hues, but also the strong base used in the dyeing process leads to deterioration of the polyurethane.
  • the object of this invention is to provide a dyeable artificial leather, particularly a dyeable grained artificial leather, having good colour fasteness, bright, deep colours, excellent lusters, soft hand and high durabilities.
  • the object can be achieved, most preferably by dyeing an artificial leather comprising a super-entangled ultrafine fiber base and PEG-type PU applied thereon with a metal dye complex.
  • the invention provides a grained artificial leather dyed with metal dye complexes and an applied fixing agent, comprising a fiber base of ultrafine polyamide fibers and/or bundles thereof of which, at a surface providing a grained surface, the fibers or bundles thereof are super-entangled, the grained surface further comprising a polyurethane applied on the super-entangled surface wherein the soft-segment constituents of the polyurethane contains at least 5% by weight of polyoxyethylene chain having molecular weight of 500-5,000.
  • the invention provides a process for manufacturing grained artificial leather, which comprises at least the following steps (1) to (5):
  • the fixing agent is selected from the group consisting of tannins, synthetic tannins and their derivatives, or tannin and metal; tannins and metal salt are used as fixing agents in another process.
  • the dyeing method makes it possible to provide deep and bright colours whilst maintaining sufficient colour fastness to enable dry cleaning of the extra-ultrafine polyamide fibers.
  • ultrafine fiber formable fibers into ultrafine fibers or bundles thereof at an appropriate stage. They can however be manufactured directly by methods such as wet spinning, super-drawing or melt-blow spinning.
  • Ultrafine fiber formable fibers include the chrysanthemum-like cross-section fibers in which one component is radially sandwiched between other components, multi-layered bicomponent fibers, radially multi-layered bicomponent hollow fibers, and islands-in-sea type composite fibers having fixed or unfixed cross section along the fiber axis. They may be used by mixing more than two of the fibers.
  • the thickness of the ultrafine fibers which can be obtained from the ultrafine fiber formable fibers should be less than 0.2 deniers (about22.2x 10 -3 tex), preferably less than 0.05 denier (about 5.55x 10- 3 tex), more preferably less than 0.01 denier (about 1.1x10 -3 tex).
  • polyamides such as nylon-6 and nylon-66, are preferable among others.
  • Polyamides et even less than 0.01 denier (about 1.11x10 -3 tex) can be deeply coloured with good colour fastness by the dyeing method stated later.
  • binding components for ultrafine fiber formable fibers
  • those readily-separable type ultrafine fiber components or those different in the solubility are selected.
  • polystyrene, polyethylene; their copolymers, and copolymerized polyesters are preferably used.
  • the copolymers of styrene with acrylic acid and/or methacrylic acid are preferable amongst them for obtaining strong fibers due to easiness of applying a high drawing ratio.
  • drawing ratio to achieve high molecular orientation or high degree of crystallinity.
  • Drawing ratio more than 2.0 times, preferably more than 2.5 times, are usually preferable, provided the spinning speeds of 600 to 1,500 m/min. (10 to 25 m/second) are used.
  • the ultrafine fibers of the grained surface should preferably have a size less than 0.2 denier (about 22.2x10 -3 tex). If not, a smooth grained surface is difficult to form because the excessive fiber stiffness affects their smoothness, the surface can produce unsightly creases and cracks, and crumpling readily causes cracks and surface unevenness.
  • the ultrafine fibers of less than 0.2 denier (about 22.2x 10- 3 tex), preferably of less than 0.05 denier (about 5.55x 10- 3 tex), more preferably of less than 0.01 denier (about 1.11 x10 -3 tex) can be densely entangled so that a surface which is highly smooth, flexible, and not liable to cause cracks, and has a soft touch feeling is obtainable.
  • the fiber structure of or just beneath the grained surface has ultrafine fibers and/or their bundles, mutually super-entangled. They should preferably be such that the distance between the fiber entanglement points (defined later) is less than 200 micrometers.
  • the fiber structures with less entanglement such as entangled only by needle punching are not preferable because they are apt to fluff or crack when subjected to friction, crumpling, or repeated shearing or bending.
  • Such fiber bases require reinforcement with a great quantity of porous resins to maintain their strength and dimensional stability and, consequently, such sheets are poor in dyeing fastness.
  • the distance between the fiber entanglement points should preferably be less than 200 micrometers or more preferably less than 100 micrometers.
  • the distance between the fiber entangelement points is defined in Laid-Open Japanese Patent application Publication No. 191280/1983 (Tokkai-sho 58-191280).
  • a short average distance between points of entanglement produces a high density of entanglement.
  • the average distance between the fiber entanglement points is measured in the following manner.
  • the fibers When observed from the surface with a scanning electron microscope, the fibers are considered to form an entanglement point when an upper fiber which has passed over and across a lower fiber then passes under and across another fiber.
  • the constituent fibers are f 1 , f 2 , f 3 , ..., the point at which two fibers f 1 and f 2 are entangled with each other is a, and another point at which the upper fiber f 2 is entangled with another fiber with the fiber f 2 being the lower fiber is a 2 (the entanglement point between f 2 and f 3 ).
  • the entanglement points a3, a4; a 5 , ...
  • the linear distances a,a 2 , a 2 a 3 , a 3 a 4 , a 4 a s , a s a e , a e a 7 , a 7 a 3 , a 3 a a , a 8 a 7 , a 7 ag, a 9 a 6 , ... measured along the surface are the distance between the fiber entangling points and their average is taken.
  • the fibers of the surface portion preferably have an average distance between the fiber entangling points of less than about 200 micrometers as measured by this method. In fiber structures where the average distance between the entangling points is greater than about 200 micrometers, such as in those fiber structures in which the entanglement of the fibers is effected only by needle punching, only little entanglement of the fibers occurs.
  • the amount of polyurethanes applied thereto can be decreased. Namely it is possible to decrease porous polyurethane to be impregnated in the fiber base or to decrease the thickness of polyurethane layer applied to the surface.
  • the fomer spoils colour fastness and the latter spoils soft hand and delicate appearance.
  • the fiber base may be nonwoven, laminated nonwoven or woven or knitted fabrics laminated and entangled with a nonwoven. Amongst them, a nonwoven fiber base comprising a surface portion of super-entangled ultrafine fibers and/or their bundles, said ultrafine fibers and/or their bundles being branched from the ultrafine bundles of the inner portion, is most preferable.
  • the degree of branching and entanglement vary at the boundary between the surface and inner portions.
  • entanglement and branching often occur throughout its thickness.
  • the dense entanglement and branching around the surface portion brings about the sheet a smooth surface and excellent stability such as against fluff and deformation.
  • Looser entanglement than the surface of the inner portion brings about softness to the sheet.
  • the amount of resin depends on the intended purposes for the leather. For clothing, however, it should preferably be Oto 50% and more preferably less than 20% based on the fiber weight.
  • the resins used for the grain layer in accordance with the invention are required to be the urethane polymers having at least 5% by weight of polyoxyethylene chains with molecular weights of 500 to 5,000 based on total weight of the soft segment. If the amount of polyoxyethylene chains is less than 5% by weight, bright colours are difficult to obtain by dyeing.
  • the molecular weight of polyoxyethylene chains is required to be 500 to 5,000 for keeping the softening temperature, resistance to flexing and solvent within their practicable range.
  • Polyurethanes whose soft segment contains polyoxyethylene chains should preferably be dyed with anionic dyes such as metal dye complexes, acid dyes and reactive dyes because they are highly affinitive thereto and particularly dyeable with metal dye complexes and have good colour fastness.
  • anionic dyes such as metal dye complexes, acid dyes and reactive dyes because they are highly affinitive thereto and particularly dyeable with metal dye complexes and have good colour fastness.
  • Polyurethane polymers in accordance with the invention are not limited to linear type and may be the cross-linked type such as cross-linked with hexamethylene diisocyanate trimer.
  • Cross-linked polyurethanes generally improve resistances to scratch, scuff, organic solvent and hot water, but is defective in flex resistance.
  • flex resistance is much improved by virtue of super-entangled surface structure.
  • the soft segment of the polyurethane may be polyoxyethylene glycol alone, but may also be its mixtures with polyether diols such as polyoxyp- roplyeneglycol, polyoxytetramethyleneglycol and polyester diols such as polyethyleneadipate, poly- butyleneadipate, polyhexamethyleneadipate and polycaprolactone, and copolymers thereof.
  • polyether diols such as polyoxyp- roplyeneglycol, polyoxytetramethyleneglycol and polyester diols
  • polyester diols such as polyethyleneadipate, poly- butyleneadipate, polyhexamethyleneadipate and polycaprolactone, and copolymers thereof.
  • PEG-type PU may be mixed with other polyurethanes so that the amount of polyoxyethylene segments is more than 5% by weight based on the total weight of the soft-segment.
  • Organic diisocyantes used to make the polyurethane include aromatic ones such as diphenylmethane-4,4'-diisocyanate, aromatic-aliphatic ones such as xylylenediisocyanate, aliphatic diisocyanates such as hexamethylenediisocyanate, and alicyclic ones such as isophoronediisocyanate and hydrogenated diphenylmethane-4,4'-diisocyanate.
  • aromatic diisocyanates, particularly diphenylmethane-4,4'-diisocyanate is preferable for obtaining good physical characateristics such as thermal stability, solution stability and fracture strength.
  • Alicyclic diisocyanates such as isophorone ones are preferably for obtaining anti-yellowed (not easily coloured even when exposed to sun) type polyurethanes.
  • Chain extenders for the polyurethane include water, low-molecular diols such as ethyleneglycol and propyleneglycol, aromatic diamines such as ethylenediamine, aliphatic diamines such as 4,4'-diaminodiphenylmethane, alicyclic diamines such as 4,4'-diaminodicyclohexylmethane and isophoronediamine, alkanolamines such as ethanolamine, hydrazines, and dihydrazide such as succinic one.
  • low-molecular diols such as ethyleneglycol and propyleneglycol
  • aromatic diamines such as ethylenediamine
  • aliphatic diamines such as 4,4'-diaminodiphenylmethane
  • alicyclic diamines such as 4,4'-diaminodicyclohexylmethane and isophoronediamine
  • alkanolamines such as
  • diamine compounds are preferable and 4,4'-diaminodiphenylmethane is particularly preferable for practical use because of its heat resistance and 4,4'-diaminodicyclohexylmethane is more preferable for light resistance. They may of course be used along or in combination.
  • the polyurethanes are generally manufactured in the presence of solvents.
  • Suitable solvents are dimethylformamide, (referred to DMF hereinunder), dimethylacetamide, ethylacetate and toluene. Amongst them DMF should be preferable used.
  • Elastomers other than polyurethane such as polyamide, polyester, polyvinyl chloride, polyacrylic ester copolymers, neoprene, styrenebutadiene copolymers, acrylonitrile-butadiene copolymers, polyamino acid, polyamino acid- polyurethane copolymers, and silicone resins may be mixed with the polyurethanes, and if necessary may be applied in lessthan 10 microns thickness to the grained surface of the present invention.
  • plasticizers, fillers, stabilizers, crosslinking agent and so forth may be added thereto.
  • the resin should be applied in great quantities to the uppermost very-thin portion of the grained surface and not at all or in small quantities to the other parts.
  • the deep luster and bright colour are obtainable by dyeing the leathers, with one or more dyes selected from anionic dyes which have a negative charge in aqueous solution such as metal dye complexes, acid dyes and reactive dyes. Further, when polyamide ultrafine fibers are used, the dyeing method described later is particularly preferable for obtaining heavy shade, and high colour fastness.
  • the colour of the urethane polymers may be improved by preliminarily adding dyes and/or pigments thereto.
  • ultrafine fibers For making ultrafine fibers, islands-in-sea type fibers are representative. It is produced, for example, by using a spinning system mentioned in Japanese Patent Application Publication No. 18369/1969 (Tokko-sho 44-18369) or dope mixed spinning.
  • ultrafine fiber formable fibers are cut into short fibers, crimped with stuffing box, formed into web and subjected to needle punching. Or, continuous filaments are spread into sheet without cutting and subjected to needle punching. Further the ultrafine fiber formable fibers may be placed on and entangled with other nonwoven, woven knitted fabrics. After that or occasionally without needle-punching, high-velocity fluid streams are applied to the sheet. Water is most preferably used amongst other fluids.
  • the branching and entanglement of the fibers are achieved through the treatment.
  • the ultrafine fiber formable fibers may be converted into bundles of ultrafine fibers before treatment with high pressure fluid streams.
  • the pressure of the fluids may be 5--100 kg/cm 2 (about 4.9-98 Bar).
  • a similar pressure may be applied for easy separable fibers.
  • 100-300 kg/cm 3 (about 98-294 Bar) is preferable for the fibers not liable to separation.
  • the degree of branching and entanglement can also be changed by contact times. Pressure may be changed each time of contact.
  • the degree of ultrafining can be controlled by treating the fiber sheets with solvents for at least a part of components. The dissolution of part of the fibers can be carried out even after impregnating or coating with resins. In this case, products become softer because many spaces where the part of components were formed along the fiber axis in the products.
  • the resin solution or dispersion for the grained surface may be applied by reverse roll coater, gravure coater, knife coater, slit coater, spraying and other methods.
  • the coated surface is pressed and if necessary heated for smoothing or embossing the surface. Sometimes pressing the fiber sheets before coating the resin is also effective for improving smoothness.
  • polyamide fibers such as nylon-6
  • nylon-6 can be dyed beautifully with acid dyes, disperse dyes or metal dye complexes.
  • ultrafine polyamide fibers less than 0.2 denier (about 22.2x 10- 3 tex) is inferior to ordinary fibers in colour fastness. This trend is remarkable for as extra-ultrafine fibers with less than 0.01 denier (about 1.11 x 1 0-3 tex).
  • the ultrafine polyamide fibers can be deeply dyed using metal dye complexes such as mordant dyes, acid mordant dyes, 1:1 metal-complex dyes, 2:1 pre-metallized dyes and metal complex direct dyes of molecular weights more than 700, more preferably of more than 900.
  • metal dye complexes such as mordant dyes, acid mordant dyes, 1:1 metal-complex dyes, 2:1 pre-metallized dyes and metal complex direct dyes of molecular weights more than 700, more preferably of more than 900.
  • the methods for this dyeing include dip drying, pad steam drying and pad drying and are not limited.
  • 2:1 premetallized dyes of larger molecular weights are easy to be produced.
  • ultrafine fibers of less than 0.01 denier (about 1.11x10 -3 tex), particularly with 0.001 denier (about 0.111 x 1 0-3 tex), can unexpectedly be dyed with so-called Irgaran- type metal complex dyes having low hydrophilicity groups such as sulfonamide and sulfon- methyl groups.
  • the metal dye complexes enhance dye bonding with the fibers by forming complex salts between the dye molecules and chrome or other metal atoms and can provide ordinary fibers with good colour fastness but in ultrafine fibers almost all colour fade by dry cleaning with charge-soap containing synthetic solvents.
  • tannins in accordance with the invention is generically given to hydrolysable tannins, condensed tannins and the complex tannins which has both properties. They are contained in the barks, leaves, roots and fruits of plants. Preferable tannins amongst them are gallotannins (tannic acid) classified in the category of hydrolytic tannins that are represented by Chiness gallotannin and gallic acid.
  • the metal salts in accordance with the invention include antimony complex salts,. iron salts, chrome salts, copper salts, bismuth salts and their complex compounds. Preferable amongst them is potassium antimonyl tartrate in the category of antimonide complex compounds.
  • Such fixing methods may be conducted by continuous 2-bath process or may be carried out by separate 2-bath process, namely, impregnation with tannins solution, drying the impregnated sheet, impregnation with metal salts solution and drying, in this order.
  • temperature can be set at 25 to 100°C. Too low temperatures lower the solubility and adsorbability of the fixing agent. On the contrary, too high temperature causes dissolving out of the absorbed dye into the treating solutions. Temperatures of 40 to 85°C, particularly 50 to 80°C, are therefore preferable and result in satisfactory fixing effects.
  • the mechanism of fixing is not known in detail, but it can be assumed that a layer of the fixing agent is formed on the surface of the ultrafine fibers and the layer multiplicatively enhances the affinity between the dyes and fibers so that dyes become difficult to move. Though such fixing treatment tends to harden the sheets, it is however also amazing that the above effects are kept even after finishing through mechnanical crumpling.
  • Such crumpling methods are not limited and include dry heat mechanical crumpling and wet heat and hot water tumbler crumpling. Further it can be carried out simultaneously with the fixing by using liquid flow dyeing machines.
  • the fiber sheets thus obtained may be futher subjected to washing and finishing agent treatment, if necessary, after the dyeing and fixing. Further the addition of polyurethanes or raising such as buffing can be applied either before or after the dyeing and fixing.
  • Surface active agent treatment is preferable for dyeing the fiber sheets impregnated with high-molecular elastomer other than PEG-type PU. That is, because other type polyurethanes suitable for impregnation are extremely inferior in colour fastness, it is rather preferable to preliminarily remove the dyes absorbed to the impregnated elastomers with surface active agents.
  • anionic, nonionic and amphoteric surfactants are effective. Particularly the latter two are preferable. Particularly preferable amongst them are polyoxyalkylene nonionic and betaine amphoteric surface active agents.
  • the former include polyoxyal- kylenealkylamine, polyoxyethylenealkylether, polyoxyethylenealkylarylether, polyoxyethylenealkylether, polyoxyethylenealkylester, poly- oxyethylenealkylamide, polyoxyethylenepolyox- ypropylene, polyoxyethylenealkylphenol and polyoxyethylenephenylether for example.
  • the fiber sheets are prepared with the multi-layered ultrafine fiber formable fibers made of polyamide and the products are subjected to multi-colour dyeing, a melange coloured product having good colour fasteness can be obtained.
  • the islands-in-sea type fiber is composed of 65 parts of acrylic acid- styrene copolymer (referred to as AS resin hereinunder) as the sea and the S-I-I component and 35 parts of nylon-6 as I-I-I component.
  • the average thickness of the I-I-I was 0.002 denier (about 0.222x10 tex).
  • a web was formed through card, cross-lapper and needle-punched with single barbed needles for entanglement.
  • the sheet has a weight 430 gr./ m 2 , an apparent density of 0.17 gr./cm 3 and an average distance between the entanglement points of 378. Both surfaces of the sheet were treated one time respectively with high-velocity fluid streams of 100 kg/cm 2 (about 98 Bar) pressure from a nozzle having 0.25 mm diameter holes arranged in one row at 2.5 mm intervals, while oscillating the nozzle.
  • the nonwoven sheet thus obtained showed the super-entangled structure in which the islands-in-sea type fibers were branched into extra ultrafine fibers and/or their bundles, and the average distance between the fiber entanglement points was 56 micrometers at the surface.
  • nonwoven sheet was shrunk in 85°C hot water, dried and smoothed between rubber roll and hot iron roll having smooth surface.
  • a prepolymer obtained from polyoxyethyleneglycol of molecular weight of 600 and isophoronediisocyanate was chain extended with 4,4'-diaminodicycylhexylmethane, terminated at the end with ethanolamine and cross-linked with 15 parts of a hexamethylenediisocyanate trimer. Then the cross-linked polyurethane was coated with gravure coater, on the smoothed surface. The amount of coating was 5 gr./m 2 . The coated surface was pressed with a hot emboss roll, for embossing and integrating the coated resin with the super-entangled surface.
  • a sheet thus obtained was subjected to dyeing and fixing using a wince dyeing machine under the following condition.
  • Dye stuff Iregalan Black GBL 200%, 10% owf.
  • Fixing agents tannic acid and tartar emetic.
  • Treating method treatment with weakly acidic bath containing 10% owf tannic acid at 50°C, for 50 min, and,
  • the sheet was softened with a tumbler crumpling machine and dried.
  • Both the grained surface and the reverse surface of thus-obtained sheet were colored dark black. It showed a softness free from undesirable rubber-like feeling and the grained surface has deep luster, resistances against scuff and repeated bending. Its washing and dry cleaning fastness according to JIS-L0844 L0860 (2% charge soap content) was good.
  • a grained artificial leather was obtained according to the same manner except using anti-yellowed (not easily coloured even when exposed to sun light) type polyester polyurethane instead of the PEG-type PU.
  • Example 2 It showed a natural leather-like appearance as that of Example 1. However the grained surface was dyed into dark-blue not into dark black. Further, the colour of the grained surface was seriously faded by dry cleaning containing 2% charge soap.
  • the same needle-punched sheet as example 1 was immersed in a 15% aqueous solution of polyvinyl alcohol (referred to PVA hereinafter) at 85°, shrunk simultaneously, dried, impregnated with a 10% DMF solution of polyester polyurethane, coagulated with 30% DMF aqueous solution and sufficiently washed in 80°C hot water for removing PVA and DMF.
  • PVA polyvinyl alcohol

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)

Claims (9)

1. Marmoriertes Kunstleder, das mit Metallfarbstoffkomplexen gefärbt und auf das ein Fixativ aufgebracht ist, aus einer Fasergrundlage aus ultrafeinen Polyamidfasern und/oder Bündeln derselben, die an einer eine marmorierte Oberfläche liefernden Fläche superverschlungen sind, wobei auf die marmorierte Oberfläche mit den Superverschlingungen ein Polyurethan, dessen Weichsegmentbestandteile mindestens 5 Gew.-% einer Polyoxyethylenkette eines Molekulargewichts von 500-5000 enthalten, appliziert ist.
2. Marmoriertes Kunstleder nach Anspruch 1, dadurch gekennzeichnet, daß es sich bei den ultrafeinen Fasern und/oder deren Bündeln um Verzweigungen von im Inneren der Fasergrundlage befindlichen ultrafeinen Faserbündeln oder ultrafeine Fasern bildenden Fasern handelt.
3. Kunstleder nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Innere der Fasergrundlage praktisch kein Harz enthält.
4. Verfahren zur Herstellung eines marmorierten Kunstleders, gekennzeichnet durch mindestens folgende Stufen (1) bis (5):
(1) Herstellen einer Faserlage, die hauptsächlich aus ultrafeinen Polyamidfasern von weniger als 22,2x10-3 tex oder ultrafeine Polyamidfasern bildenden Fasern besteht;
(2) Verschlingen der Faserlagen durch Einwirkenlassen von Hochgeschwindigkeitsfluidumströmen auf mindestens eine ihrer Oberflächen zur Ausbildung einer superverschlungenen Oberfläche;
(3) Aufbringen eines Polyurethans, dessen Weichsegmentbestandteile mindestens 5 Gew.-% einer Polyoxyethylenkette eines Molekulargewichts von 500-5000 enthalten, auf die superverschlungene Oberfläche zur Ausbildung einer marmorierten Oberfläche;
(4) Anfärben der Lage aus einer Fasergrundlage und dem applizierten Polyurethan mit mindestens einem Metallfarbstoffkomplex und
(5) Aufbringen eines Fixativs.
5. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß das Fixativ aus Tanninen, künstlichen Tanninen und deren Derivaten ausgewählt ist.
6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß als Fixative Tannin und en Metallsalz verwendet werden.
7. Verfahren nach Anspruch 4, dadurch gekenzeichnet, daß der Metallfarbstoffkomplex ein Molekulargewicht von über 700 aufweist.
8. Verfahren nach Anspruch 4, dadurch gekennzeichnet, daß es sich bei dem Metallfarbstoffkomplex um einen 2:1 vormetallisierten Farbstoff handelt.
9. Verfahren zur Herstellung eines Kunstleders nach Anspruch 4, dadurch gekennzeichnet, daß nach dem Anfärben eine Knitterbehandlung durchgeführt wird.
EP19840304074 1983-02-10 1984-06-16 Narbenkunstleder mit einer guten Farbechtheit und Verfahren zum Färben von ultrafeinen Polyamidfasern Expired EP0165345B1 (de)

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DE8484304074T DE3479524D1 (en) 1984-06-16 1984-06-16 Grained artificial leather having good colour fastness and dyeing method of ultrafine polyamide fibers

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JP2099383A JPS59150133A (ja) 1983-02-10 1983-02-10 皮革状ヤ−ン

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EP0165345B1 true EP0165345B1 (de) 1989-08-23

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Cited By (1)

* Cited by examiner, † Cited by third party
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Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0305596B1 (de) * 1983-02-10 1992-01-15 Toray Industries, Inc. Verfahren zum F rbe von ultrafeinen Polyamidfasern
JPS59168143A (ja) * 1983-03-15 1984-09-21 旭化成株式会社 織編組物用材料
JPS612468U (ja) * 1984-06-08 1986-01-09 東レ株式会社 特殊風合糸
IT1211465B (it) * 1987-06-19 1989-11-03 Lorica Spa Procedimento per ottenere un pellame scamosciato sintetico simile a quello naturale
JPH07873B2 (ja) * 1989-03-27 1995-01-11 株式会社クラレ 着色された人工皮革
DE9306719U1 (de) * 1993-05-04 1993-07-08 Nabinger, Udo, 67468 Frankenstein Technisches Leder für Sportbälle
CN1067451C (zh) * 1993-10-29 2001-06-20 可乐丽股份有限公司 绒面人造革
KR101523394B1 (ko) 2007-03-30 2015-05-27 가부시키가이샤 구라레 은 부조 피혁양 시트 및 그 제조 방법
CN110387029A (zh) * 2019-08-01 2019-10-29 南通市联缘染业有限公司 一种阴离子型全棉筒子纱染色专用固色剂的制备方法
WO2022070953A1 (ja) * 2020-09-29 2022-04-07 東レ株式会社 人工皮革およびこれを用いてなる光透過デバイス
CN112341597B (zh) * 2020-10-30 2022-09-16 西安工程大学 一种水性聚氨酯湿摩擦牢度提升剂的制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3899292A (en) * 1972-03-23 1975-08-12 Toray Industries Process for crumpling synthetic suede
JPS539301A (en) * 1976-07-12 1978-01-27 Mitsubishi Rayon Co Production of leather like sheet structre
JPS5928670B2 (ja) * 1977-09-06 1984-07-14 帝人株式会社 皮革様構造物の製造方法
JPS5942627B2 (ja) * 1979-07-31 1984-10-16 豊田合成株式会社 幅射熱遮蔽透明シ−ト
JPS56145948A (en) * 1980-04-15 1981-11-13 Kuraray Co Ltd Polyurethane composition suitable for synthetic leather
DE3314478A1 (de) * 1982-04-29 1983-11-03 Sandoz-Patent-GmbH, 7850 Lörrach Verfahren zum faerben von voluminoesen textilien

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT202000031787A1 (it) * 2020-12-22 2022-06-22 Colonna S P A Processo per la produzione di un materiale similpelle bio-based e vegan
EP4033027A1 (de) * 2020-12-22 2022-07-27 Colonna S.p.A. Verfahren zur herstellung eines biobasierten und veganen kunstledermaterials

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