EP3202976B1 - Suede type artificial leather with soiling protection property and preparation therefor - Google Patents

Suede type artificial leather with soiling protection property and preparation therefor Download PDF

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Publication number
EP3202976B1
EP3202976B1 EP15846907.2A EP15846907A EP3202976B1 EP 3202976 B1 EP3202976 B1 EP 3202976B1 EP 15846907 A EP15846907 A EP 15846907A EP 3202976 B1 EP3202976 B1 EP 3202976B1
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Prior art keywords
fluorine
artificial leather
modified polyurethane
containing modified
molecular weight
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German (de)
English (en)
French (fr)
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EP3202976A1 (en
EP3202976A4 (en
Inventor
Hyuk-jae YOU
Gyoung-cherl GO
Dae-Young Jung
Zhequan PIAO
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Kolon Industries Inc
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Kolon Industries Inc
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    • 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
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N3/0002—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
    • D06N3/0011—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 non-woven 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
    • 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
    • D06N3/004—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 flocked webs or pile fabrics upon which a resin is applied; Teasing, raising web before resin application
    • 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
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
    • 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
    • D06N3/12—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
    • D06N3/147—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 characterised by the isocyanates used
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/12—Permeability or impermeability properties
    • D06N2209/126—Permeability to liquids, absorption
    • D06N2209/128—Non-permeable
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/142—Hydrophobic
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/146—Soilproof, soil repellent
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/14—Properties of the materials having chemical properties
    • D06N2209/147—Stainproof, stain repellent
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/904—Artificial leather

Definitions

  • the present invention relates to a suede type artificial leather having soiling protection properties, and more particularly to a simple method of preparing an artificial leather impregnated with a modified polyurethane having an soiling protection property, which the addition of an additive having an soiling protection function is not needful.
  • Artificial leather is prepared by impregnating a polymer elastomer in a nonwoven fabric formed by three-dimensionally interlacing ultrafine fibers.
  • the artificial leather has a smooth texture and unique appearance which is similar to natural leather and is widely used in various fields such as shoes, clothes, gloves, miscellaneous goods, furniture and automobile interior materials.
  • Artificial leather requires various characteristics according to its use.
  • the properties required for artificial leather for clothing include high durability, high sensitivity, excellent dyeability which can be stained with various colors and concentrations and high fastness.
  • artificial leather is required to be provided with an soiling protection function including a water-repellent and oil-repellent function for inhibiting the occurrence of fouling even after a long-term use.
  • a fluorine-based or silicone-based surfactant can be mixed with polyurethane and a mixture can be impregnated in a nonwoven fabric, thereby arranging a fluorine chain or a silicone chain on the surface of the artificial leather. The occurrence of fouling can be suppressed from the outside of the artificial leather accordingly.
  • fluorine-based or silicone-based surfactants are generally inactive additives, and in case that they are mixed with polyurethane, there is a problem that they are not chemically bonded to each other, thus they are free to move in the urethane molecular structure and as a result, transition of the surfactants to the surface of artificial leather occurs causing a surface change with the passage of time thereof.
  • Korean Patent No. KR100969839 B discloses a modified urethane to which fluorine is bonded and a method of preparing leathery sheet object using the modified urethane without the addition of a fluorine-based compound.
  • the urethane compound modified with fluorine-containing side chain is used together with polyurethane which is an elastomer constituting the treatment liquid of a leathery sheet object, and exhibits an effect as a water-repellent agent as an additive.
  • EP 1 143 063 A2 discloses an artificial leather having a base sheet impregnated with a resin layer comprising a polyurethane having side chains derived from a fluorine-containing diol.
  • an object of the present invention is to provide artificial leather impregnated with a novel modified polyurethane, having an soiling protection property without adding an additive having an soiling protection property.
  • an aspect of the present invention provides a suede type artificial leather according to claim 1, having soiling protection property in which a polymeric elastomer is impregnated in a nonwoven fabric formed by three-dimensionally interlacing ultrafine fibers and raising is formed, wherein the polymeric elastomer is a fluorine-containing modified polyurethane, and the fluorine-containing modified polyurethane is a product obtained by a polymerization reaction between a urethane prepolymer having isocyanate groups at terminals, obtained by reacting a diol and a diisocyanate, and a fluorinated carbon compound having hydroxy functional groups at both terminals, and has a weight average molecular weight (Mw) of 500,000 to 800,000, wherein the urethane prepolymer has a weight average molecular weight (Mw) of 400,000 to 700,000.
  • Mw weight average molecular weight
  • the present invention also provides a method of preparing a suede type artificial leather according to claim 2, having soiling protection property in which a polymeric elastomer is impregnated in a nonwoven fabric formed by three-dimensionally interlacing ultrafine fibers and raising is formed, wherein the polymeric elastomer is a fluorine-containing modified polyurethane, and the fluorine-containing modified polyurethane is prepared by a method comprising: preparing a urethane prepolymer having a weight average molecular weight (Mw) of 400,000 to 700,000 by reacting a diol and a diisocyanate; and preparing a polymerization product having a weight average molecular weight (Mw) of 500,000 to 800,000 by reacting the prepolymer and a fluorinated carbon compound having hydroxy functional groups at both terminals.
  • Mw weight average molecular weight
  • artificial leather impregnated with a fluorine-containing modified polyurethane elastomer having soiling protection property also exhibits excellent water repellency in addition to the soiling protection property.
  • the artificial leather of the present invention can decrease the surface change with the passage of time, as compared with artificial leather produced by separately adding a fluorine-containing surfactant having the large occurrence of surface change with the passage of time due to the migration of the surfactant.
  • the present invention relates to a suede type artificial leather having soiling protection property in which a polymeric elastomer is impregnated in a nonwoven fabric formed by three-dimensionally interlacing ultrafine fibers and raising is formed, wherein the polymeric elastomer is a fluorine-containing modified polyurethane.
  • the fluorine-containing modified polyurethane is a product obtained by a polymerization reaction between a urethane prepolymer having isocyanate groups at terminals and a weight average molecular weight (Mw) of 400,000 to 700,000, obtained by reacting a diol and a diisocyanate, and a fluorinated carbon compound having hydroxy functional groups at both terminals, and has a weight average molecular weight (Mw) of 500,000 to 800,000.
  • the diol may be used alone or in combination with diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • diols such as 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, ethylene glycol, diethylene glycol, polyethylene glycol, polypropylene glycol or polytetramethylene glycol.
  • the diisocyanate may be 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodecamethylene diisocyanate, cyclohexane-1,3- to 1,4-diisocyanate, 1-isocyanate-3-isocyanatemethyl-3,5,5-trimethylcyclohexane(isophorone diisocyanate), bis-(4-isocyanatecyclohexyl) methane(hydrogenated MDI), 2- to 4-isocyanatecyclohexyl-2-isocyanatecyclohexylmethane, 1,3- to 1,4-tetramethylxylene diisocyanate, 2,4-to 2,6-diisocyanate toluene, 2,2-2,4- to 4,4'-diphenylmethane diisocyanate , 1,5-naphthalene diisocyanate, xylene diisocyanate or diphenyl-4,
  • the proportion to be reacted needs an excess amount of all NCO groups rather than all OH groups.
  • the resulting urethane prepolymer may have an isocyanate group terminal in side chains thereof.
  • the molar ratio of the diol and the diisocyanate is preferably 1:1.2 to 1:1.4 because the fluorine-containing modified polyurethane having the weight average molecular weight range of the present invention can be produced.
  • the molar ratio When the molar ratio is less than 1:1.2, a side reaction occurs due to moisture or active hydrogen, etc. in the air, or the isocyanate reacts with each other to manifest a property of isocyanate for forming a trimer and to decrease the polymerization efficiency due to the increase of inactive NCO.
  • the molar ratio is more than 1:1.4, the excess of NCO groups causes an insufficient OH group so that it is difficult to raise the degree of polymerization.
  • a urethane prepolymer can be prepared first.
  • the weight average molecular weight (Mw) of the urethane prepolymer is less than 400,000, the molecular weight of the fluorine-containing modified polyurethane is lowered, and the mechanical properties such as tear strength, etc. and the chemical properties such as thermal stability and hydrolysis resistance, etc. are lowered. If it exceeds 700,000, the gelation phenomenon may occur in the production of the fluorine-containing modified polyurethane, and the viscosity of the fluorine-containing modified polyurethane may be high to reduce the workability in blending of an elastomer impregnation solution, and the resulting fluorine-containing modified polyurethane may be hardened, which may deteriorate the sensual quality in artificial leather.
  • the fluorinated carbon compound having hydroxy functional groups at both terminals is represented by the following Chemical Formula 1, has 8 to 14 fluorine groups bonded to one side chain and fluorine content of 50 to 70mol% in one functional group and is an ether diol having hydroxy functional groups at both terminals.
  • Chemical Formula 1 HO-CH 2 -CF 2 -O- (CF 2 CF 2 O) m- (CF 2 O) n-CF 2 -CH 2 -OH
  • the fluorine-containing modified polyurethane obtained by reacting the ether diol of the Chemical Formula 1 with the urethane prepolymer can provide water-repellent and oil-repellent functions because the fluorine which is present as the diatomic molecule in the element state, in the side chain of the urethane polymer is bonded to prevent that the modified polyurethane is bonded to other atoms or molecules.
  • the fluorine-containing modified polyurethane of the present invention the artificial leather can be suppressed deposition of an external contaminant and easily removed contaminants on the coated surface.
  • a commercialized product of a fluorinated carbon compound having hydroxy functional groups at both terminals is Solvay's FLUOROLINK.
  • the polymerization of the fluorine-containing modified polyurethane of the present invention can be carried out through the addition-polymerization by adding dropwise the fluorinated carbon compound having hydroxy functional groups at both terminals to the urethane prepolymer until the desirable molecular weight is reached. At this time, the addition amount of the fluorinated carbon compound corresponds to the moles of excess isocyanate in preparing the urethane prepolymer.
  • the fluorine-containing modified polyurethane of the present invention is polymerized by the above-mentioned method and is characterized by having a weight average molecular weight (Mw) of 500,000 to 800,000. If the weight average molecular weight (Mw) is less than 500,000, the mechanical strength such as tear strength, etc. and chemical properties such as thermal stability, hydrolysis resistance, and the like in artificial leather may be reduced.
  • Mw weight average molecular weight
  • the viscosity of the fluorine-containing modified polyurethane may be high to reduce the workability in blending of an elastomer impregnation solution, and the resulting fluorine-containing modified polyurethane may be hardened, which may deteriorate the sensual quality in artificial leather.
  • the fluorine-containing modified polyurethane of the present invention has a fluorine content of 5 to 20mol%.
  • the content is less than 5mol%, the soiling protection performance is insufficient, and when the content is more than 20mol%, the water repellency is too strong so that the fluorine-containing modified polyurethane cannot undergo the substitution solidification in the manufacturing process of the artificial leather.
  • R and R' are each independently an alkyl group.
  • artificial leather can be prepared by immersing a nonwoven fabric formed by three-dimensionally interlacing ultrafine fibers in an impregnating liquid comprising a polymeric elastomer such as polyurethane, impregnating the polymeric elastomer to solidify the elastomer in the nonwoven fabric, raising by grinding and dyeing.
  • an impregnating liquid comprising a polymeric elastomer such as polyurethane
  • the fluorine-containing modified polyurethane of the present invention can be used as a polymeric elastomer of the impregnating liquid.
  • the fluorine-containing modified polyurethane may be used as an impregnating liquid by diluting it in dimethyl formamide of 100 to 200wt% in respect of the weight of the fluorine-containing modified polyurethane.
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.2mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 40% by weight to prepare an NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 700,000.
  • the prepared prepolymer was subjected to addition polymerization with 0.2mol of a fluorinated carbon compound having hydroxy functional groups at both terminals in a side chain (trade name: FLUOROLINK D10-H, manufactured by Solvay, Mw: 1,400) and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 30% by weight to prepare a fluorine-containing modified polyurethane having a weight average molecular weight (Mw) of 800,000.
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.3mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 40% by weight to prepare an NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 600,000.
  • the prepared prepolymer was subjected to addition polymerization with 0.3mol of a fluorinated carbon compound having hydroxy functional groups at both terminals in a side chain (trade name: FLUOROLINK D10-H, manufactured by Solvay, Mw: 1,400) and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 30% by weight to prepare a fluorine-containing modified polyurethane having a weight average molecular weight (Mw) of 700,000.
  • a fluorinated carbon compound having hydroxy functional groups at both terminals in a side chain trade name: FLUOROLINK D10-H, manufactured by Solvay, Mw: 1,400
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.4mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 40% by weight to prepare an NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 400,000.
  • the prepared prepolymer was subjected to addition polymerization with 0.4mol of a fluorinated carbon compound having hydroxy functional groups at both terminals in a side chain and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 30% by weight to prepare a fluorine-containing modified polyurethane having a weight average molecular weight (Mw) of 500,000.
  • Mw weight average molecular weight
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.0mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 70% by weight to prepare a reaction-terminated polyurethane having a weight average molecular weight (Mw) of 700,000.
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.7mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 40% by weight to prepare an NCO-terminated polyurethane prepolymer having a weight average molecular weight (Mw) of 350,000.
  • the prepared prepolymer was subjected to addition polymerization with 0.7mol of a fluorinated carbon compound having hydroxy functional groups at both terminals in a side chain and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 30% by weight to prepare a fluorine-containing modified polyurethane having a weight average molecular weight (Mw) of 450,000.
  • Mw weight average molecular weight
  • Polytetramethylene glycol (Mw: 1,500-2,500) of 0.45mol, ethylene glycol of 0.47mol and 1,4-butanediol of 0.08mol were subjected to addition polymerization with 1.0mol of 4,4'-diphenylmethane diisocyanate, and the produced polymerization product was diluted and dissolved in dimethylformamide so as to be a total solid content of 70% by weight to prepare a reaction-terminated polyurethane having a weight average molecular weight (Mw) of 700,000.
  • the fluorine-containing modified polyurethane of the Preparation Example 1 was diluted with 150% by weight of dimethylformamide in respect of the weight of the polyurethane to prepare an impregnating liquid.
  • the nonwoven fabric in which the polyester fibers (0.3 denier, fiber length: 51mm) was entangled was immersed in the impregnation solution, taken out and carried out coagulating process in an aqueous solution diluted with 20% by weight of dimethylformamide to form the fluorine-containing modified polyurethane elastomer impregnated nonwoven fabric in which a fine porous layer was formed in the fiber structure.
  • a suede type artificial leather was produced in the same manner as in Example 1, except that the fluorine-containing modified polyurethane of Preparation Example 2 was used to prepare an impregnation solution.
  • a suede type artificial leather was produced in the same manner as in Example 1, except that the fluorine-containing modified polyurethane of Preparation Example 3 was used to prepare an impregnation solution.
  • a suede type artificial leather was produced in the same manner as in Example 1, except that the fluorine-containing modified polyurethane of Preparation Example 4 was used to prepare an impregnation solution.
  • a suede type artificial leather was produced in the same manner as in Example 1, except that the fluorine-containing modified polyurethane of Preparation Example 5 was used to prepare an impregnation solution.
  • a suede type artificial leather was produced in the same manner as in Example 1, except that the reaction-terminated polyurethane of Preparation Example 6 is diluted with a mixture of 150% by weight of dimethylformamide and 0.5% of a fluorine-based surfactant (trade name FC-4430, 3M) with respect of the weight of the polyurethane, to prepare an impregnation solution.
  • a fluorine-based surfactant trade name FC-4430, 3M
  • the weight average molecular weights (Mw) of the polymer prepared in the above Examples and Comparative Examples were measured using gel permeation chromatography (GPC) (RI-8000, manufactured by Tosoh Corporation) passing through the column connected TSKgel super HM-L, TSKgel super HM-M and TSKgel super HM-N (Tosoh) in series with tetrahydrofuran (flow rate: 1mL/min) as a mobile phase and the column oven at temperature of 40 °C.
  • GPC gel permeation chromatography
  • An artificial leather sample was cut into a size of 5x15cm and placed in a rubbing fastness tester (model name DL-2007) and a test fabric (product name: IEC carbon black/mineral oil, manufactured by EMPA) was placed on the surface of the fouled sample and rubbed by 10 times reciprocating motion, and the soiled sample was visually compared to give a soiling degree.
  • a rubbing fastness tester model name DL-2007
  • a test fabric product name: IEC carbon black/mineral oil, manufactured by EMPA
  • the artificial leather of the Example according to the present invention in which the fluorine-containing modified polyurethane is impregnated as an elastomer has the same soiling protection performance as the artificial leather (Comparative Example 3) in which the fluorine-containing surfactant was separately added, and exhibits improved water repellency at the same time.
  • the artificial leather according to the present invention is an artificial leather in which a fluorine-containing modified polyurethane having an soiling protection property is impregnated.
  • the fluorine-containing surfactant does not need separately for the soiling protection property during the production of artificial leather so that productivity increase is possible.
  • the artificial leather according to the present invention exhibits an excellent soiling protection performance that suppresses the surface change with the passage of time of the artificial leather caused by using a fluorine-containing surfactant, thereby improving the appearance quality of the artificial leather.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Polyurethanes Or Polyureas (AREA)
EP15846907.2A 2014-09-29 2015-09-23 Suede type artificial leather with soiling protection property and preparation therefor Active EP3202976B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020140130226A KR101963127B1 (ko) 2014-09-29 2014-09-29 방오성을 가지는 스웨이드형 인공피혁의 제조방법
PCT/KR2015/009995 WO2016052906A1 (ko) 2014-09-29 2015-09-23 방오성을 가지는 스웨이드형 인공피혁 및 이의 제조방법

Publications (3)

Publication Number Publication Date
EP3202976A1 EP3202976A1 (en) 2017-08-09
EP3202976A4 EP3202976A4 (en) 2018-05-30
EP3202976B1 true EP3202976B1 (en) 2019-06-12

Family

ID=55630882

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Application Number Title Priority Date Filing Date
EP15846907.2A Active EP3202976B1 (en) 2014-09-29 2015-09-23 Suede type artificial leather with soiling protection property and preparation therefor

Country Status (6)

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US (1) US20170284018A1 (ko)
EP (1) EP3202976B1 (ko)
JP (1) JP6530810B2 (ko)
KR (1) KR101963127B1 (ko)
CN (1) CN107075792A (ko)
WO (1) WO2016052906A1 (ko)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101619636B1 (ko) 2014-11-07 2016-05-10 현대자동차주식회사 내구성이 향상된 스티어링 휠 커버용 인조 피혁 및 그 제조방법
WO2018215386A1 (en) * 2017-05-24 2018-11-29 Solvay Specialty Polymers Italy S.P.A. Monolithic breathable membrane

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0674546B2 (ja) * 1986-04-25 1994-09-21 大日精化工業株式会社 擬 革
IT1213441B (it) * 1986-12-30 1989-12-20 Ausimont Spa Dispersioni acquose di poliuretani e fluorurati e loro impiego per spalmature tessili.
KR940011516B1 (ko) * 1991-06-07 1994-12-20 주식회사 금성사 칼라비디오 프린터의 노광장치
JP3121457B2 (ja) * 1992-10-30 2000-12-25 株式会社クラレ 耐汚染性の良い皮革様シート
KR960006297B1 (ko) * 1992-11-11 1996-05-13 동양나이론주식회사 인공피혁용 폴리우레탄 수지 조성물
EP1143063B1 (en) * 2000-03-31 2008-09-17 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Artificial leather
KR100969839B1 (ko) * 2002-06-20 2010-07-13 데이진 고도레 가부시키가이샤 피혁 유사 시트형물, 그 제조방법 및 불소 함유 측쇄 변성 우레탄 화합물
DE10331483A1 (de) * 2003-07-11 2005-02-10 Construction Research & Technology Gmbh Fluormodifizierte ein- oder zweikomponentige Polyurethanharze, Verfahren zu ihrer Herstellung und deren Verwendung
DE102009014699A1 (de) * 2009-03-27 2010-10-07 Carl Freudenberg Kg Verfahren zur Herstellung einer reaktiven Polyurethan-Emulsion
EP2719713B1 (en) * 2011-06-13 2018-10-03 DIC Corporation Polyurethane composition, water repellent agent, polyurethane resin composition for forming surface skin layer of leather-like sheet, and leather-like sheet
KR20130035369A (ko) * 2011-09-30 2013-04-09 코오롱인더스트리 주식회사 인공피혁 및 그의 제조방법

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Publication number Publication date
JP2017534773A (ja) 2017-11-24
WO2016052906A1 (ko) 2016-04-07
KR101963127B1 (ko) 2019-03-28
EP3202976A1 (en) 2017-08-09
EP3202976A4 (en) 2018-05-30
KR20160037538A (ko) 2016-04-06
CN107075792A (zh) 2017-08-18
JP6530810B2 (ja) 2019-06-12
US20170284018A1 (en) 2017-10-05

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