US3841897A - Artificial leather - Google Patents

Artificial leather Download PDF

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US3841897A
US3841897A US00298449A US29844972A US3841897A US 3841897 A US3841897 A US 3841897A US 00298449 A US00298449 A US 00298449A US 29844972 A US29844972 A US 29844972A US 3841897 A US3841897 A US 3841897A
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artificial leather
coating layer
polymer
iii
weight
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K Okazaki
A Higuchi
N Imaeda
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Toray Industries Inc
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Toray Industries Inc
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Priority to US00298449A priority Critical patent/US3841897A/en
Priority to FR7237691A priority patent/FR2203901B1/fr
Priority to GB4920572A priority patent/GB1412261A/en
Priority to US45191574 priority patent/US3908060A/en
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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
    • 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
    • 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.]
    • Y10T428/24446—Wrinkled, creased, crinkled or creped
    • 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.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/2495—Thickness [relative or absolute]
    • Y10T428/24967—Absolute thicknesses specified
    • Y10T428/24975—No layer or component greater than 5 mils thick
    • 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.]
    • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
    • Y10T428/24992—Density or compression of components
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/254—Polymeric or resinous material
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
    • 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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31554—Next to second layer of polyamidoester
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31609—Particulate metal or metal compound-containing

Definitions

  • Bell Artificial leather is composed of four layers: a fibrous substrate, a urethane polymer layer (111) containing finely divided inorganic particles, a thinner urethane polymer layer (11) consisting of at least about 80 percent by weight of polyurethane, and a coating layer (1) consisting of at least about 80 percent by weight of polyurethane.
  • This invention is concerned with artificial leather and a method for its preparation. More particularly, this in- PRIOR ART
  • a fibrous substrate has been prepared from a non-woven fabric, or a woven or knitted fabric impregnated with a impregnating composition.
  • a microporous polymeric coating layer is applied to provide a composite structure having two layers. It is said that peculiar properties of artificial leather such as water vapor permeability, water vapor absorption, surface-smoothness, appearance and feeling, etc.
  • Another object of this invention is to provide a manufacturing method which is advantageous in industrial production.
  • the coating layer (1) has a thickness of about 0.001 to 0.1 mm and a 20 percent modulus of about 5 to 100 kg/cm and consists of a polymer composition containing at least about wt% of polyurethane.
  • the coating layer (11), obtained by the wetcoagulating method, has a thickness of about 0.01 to 0.3 mm, consists of polymer composition which contains 0 to 50 parts by weight of inorganic particles for each parts by weight of polymer (coagulation stabilizer is excluded from this polymer this definition is used through to the end). These inorganic particles have a mean particle diameter of about 0.03 to 5.0 micron, and are insoluble in water, and the polymer consists of at least about 80 wt% of polyurethane.
  • Coating layer (111) obtained by the wet-coagulating method, has a thickness of about 0.1 to 3.0 mm, consists'of polymer composition which contains about 50 to 300 parts by weight of inorganic particles for each 100 parts by weight of polymer (coagulation stabilizer is excluded from this polymer this definition is used through to the end), and-these inorganic particles have a mean particle of about 0.03 to 5.0 micron, and are insoluble in water, and the polymer consists of at least about 60 wt% of polyurethane.
  • the role of the agglutination protecting agent is to protect the microporous structure from changing to a non-porous structure.
  • the fibrous substrate has a thickness of about 0.3 to 3.0 mm and consists of at least a polymer and a fabric, which may be non-woven, knitted or woven. Coating layers (1), (II), (III) and the fibrous substrate are joined to one another in order, by the method to be described in detail hereinafter.
  • FIG. 1 an example of the cross-sections of the artificial leather of this invention is illustrated.
  • (1) is the coating layer (1)
  • (2) is the coating layer (II)
  • (3) is the coating layer (111)
  • (4) is the fibrous substrate composed of a fabric impregnated with a polymer composition.
  • the multi-coating layer consists of coating layers (I), (I1), and (111).
  • FIG. 2 shows the measurement of 6, the creaseforming angle referred to in tests of the artificial leather
  • FIG. 3 is a diagrammatic illustration of a part of a method for testing flexibility resistance of artificial leather.
  • the polymer contained in coating layer (1) and (II) used in this invention is composed of (a) polyurethane or (b) more than about 80 wt% of polyurethane and less than about 20 wt%of a polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyacrylic acid, alkylpolyacrylate, polymethaerylic acid, alkylpolymethacrylate, and copolymers consisting of at least of one of the above mentioned polymer segments, and
  • the polyurethane contained in coating layers (I), (ll) and (ill) used in this invention is (e) the product of reaction of polymer diols, di-isocyanates and diamines and/or lower molecular diols, wherein the polymer diol is selected from the group consisting of poly-etherdiols, poly-ester-diols and poly-ether-ester-diols.
  • the polymer contained in the impregnating composition used in this invention is as follows: .(f) the polyurethane of (e) or (g) a polymer selected from the group consisting of polyvinyl chloride, copolymers of vinyl chloride and vinyl acetate, polyacrylic acid and its esters, and polymethacrylic acid and its esters, or (h) mixtures of more than about 50 wt% of polyurethane of (e) and less than about 50 wt% of the polymers mentioned in (g).
  • polymer compositions for coating layers (i), (ll), (lll) and impregnating compositions such addition compounds as pigments, dyes, anti-oxidants, pulp powders, fiberpowders, etc. may be added.
  • the inorganic compounds contained in the above coating compositions (ll) and (Ill), used in this invention are as follows: calcium carbonate, titanium oxide, zinc oxide, kaolinite, carbonates (such as .zinc'carbonate, cadmium carbonate, copper carbonate, barium carbonate, etc.),- oxides (such as chromium oxide, aluminium'oxide, antimony oxide, cobalt oxide, tin oxide, iron oxide, etc.), sulfates (such as calcium sulfate, barium sulfate, etc.
  • phosphates such as zinc phosphate, aluminium phosphate, calcium monohydrogen phosphate, ferrous phosphate, barium phosphate, etc.
  • silicates such ascobalt silicate, magnesium silicate, potassium alumino silicate, kaolin, etc.
  • inorganic compounds used in this invention are calcium carbon ate, titanium oxide, zinc oxide and kaolinite.
  • the inorganic compounds for coating layers (ll) and (Ill) used in this invention must be insoluble in water and organic solvents, so that-said inorganic compounds do not dissolve out of the coating layers (ll) and (Ill). However, some substance in coating layer ([1) and (III) must dissolve during the process of coating polymer composition. (l) on the surface of coating layer (ll). This causes the surface of coating layer (ll) to'become rough, and as a result of this process, creases are formed when the artificial leather thus obtained is bent or flexed.
  • the amount of inorganic compounds, and the mean particle diameter of inorganic compounds are very important in order to obtain various kinds of creases with precision control.
  • the satisfactory range of the mean particle diameter of said inorganic compounds in-coating layers (ll) and (Ill) is about 0.03 to 5.0 micron, more satisfactory about 0.10 to 3.0 micron, and most satisfactory about 0.5 to 2.0 micron.
  • a diameter larger than about 5.0 micron the apppearance of creases is no longer that of natural leather, and the state of dispersion of inorganic compounds in polymer composition for coating layer, flexibility resistance and scuff resistance become worse, and suitable physical properties and homogeneous structure of the leather cannot be obtained.
  • a diameter of smaller than about 0.03 micron the appearance of creases is not that of natural leather, and water vapor permeability and softness become worse. This will be confirmed in a detailed explanation in describing the following experiments. They show the criticality of the above mentioned ranges of mean particle diameter.
  • the satisfactory range of the amount of inorganic compounds in coating layer (lll) is about 50 to 300 parts by weight for each parts by weight of polymer in the coating layer, more satisfactory about 80 to 200 parts, and most satisfactory about to parts.
  • the mechanical properties of coating layer (lll) such as tensile strength, elongation, tear and scuff resistance, etc., become worse, and the durability of the artificial leather also becomes worse.
  • the case of an amount of less than about 50 parts in the coating layer (lll the appearance of creases is not that of natural leather, and the appearance and feel are similar to those of rubber, and the properties and performance of the artificial leather in this case are those of artificial leatherhitherto obtained.
  • the satisfactory range of thickness of coating layer (lll) is about 0.1 to 3.0 mm, more satisfactory about 0.3 to 2.0 mm, and most satisfactory about 0.5 to 1.0 mm.
  • a thickness of coating layer (lll) largerthan about 3.0 mm, and comparatively less inorganic compounds in the coating layer (lll) at the same time the properties of artificial leather obtained are similar to those of rubber.
  • the mechanical properties of the coating layer and the artificial leather become worse.
  • a thickness of coating layer (lll) smaller than about 0.1 mm the smoothness of the artificial leather become worse and the appearance of creases in the artificial leather obtained is not that of natural leather.
  • a satisfactory range of amounts of inorganic compounds in coating layer (ll) is about 0 to 50 parts by weight for each 100 parts by weight of polymer in coat ing layer (II), more satisfactory about 0 to 20 parts, and the most satisfactory none at all. in the case of an amount more than 50 parts in coating layer (ll), the appearance of creases of artifical leather obtained is not that'of natural leather.
  • a satisfactory range of thickness of coating layer (ii) is about 0.01 to 0.3 mm, more satisfactory about 0.03 to 0.25 mm, and the most satisfactory about 0.05 to 0.2 mm.
  • Coating layer (l) is prepared by a dry-coagulating method. Coating layer (l) is coated on coating layer (II) and dried to remove solvent.
  • the satisfactory range of thickness of coating layer (I) is about 0.001 to 0.1 mm, more satisfactory about 0.003 to 0.05 mm, and the most satisfactory about 0.005 to 0.02 mm.
  • the satisfactory range of 20 percent modulus ofcoating layer (I) is about 5 to 100 kg/cm more satisfactory about to 70 kg/cm and the most satisfactory about to 50 kglcm The method of the measurement of percent modulus is described hereinafter.
  • a thickness of coating layer of smaller than 0.001 mm the color and luster of the artificial leather is unsatisfactory, and creases cannot be formed, and scuff resistance decreases.
  • a thickness of coating layer (I) larger than 0.3 mm the appearance of creases and the feeling and appearance of the artificial leather obtained are not those of natural leather (the appearance of creases becomes too small), and water vapor permeability and flexibility resistance become worse, and the touch of the artificial leather becomes hand.
  • Coating layer (II) and (III) are prepared by a wetcoagulating method, and the detailed method of preparation of coating layer (II) and (III) is described hereinafter.
  • coating layers (II) and (III) can be prepared from a polymer composition excluding non-solvents such as water. But when the polymer composition is used as a coating layer immediately after the polymer composition has been prepared, a small amount of non-solvent such as water in the polymer composition may be permitted.
  • the artificial leather of this. invention has a multi-layer structure composed of coating layers (I), (II) and (III).
  • This multi-layer structure with a fibrous substrate brings about the appearance of the creases like that of natural leather, particularly German Box Calf.
  • the satisfactory range of thickness of the multi-layer coating (I), (II) and (III) of this invention is about 0.1 to 3.6 mm, more satisfactory about 0.3 to 2.0 mm, and the most satisfactory about 0.5 to 1.5 mm.
  • a thickness of the multi-layer of larger than about 3.6 mm the appearance and feel of the artificial leather obtained arenot like those of natural leather.
  • a thickness of the multi-layer of less than about 0.1 mm the appearance of creases of the artificial leather obtained is not that of natural leather. 7
  • the apparent density of coating layer (III) is larger than that of coating layer (II).
  • a satisfactory range of the apparent density difference between coating layer (III) and (II) is about 0.05 to 0.8 g/cm, more satisfactory about 0.07 to.0.6 glcm and the most satisfactory about 0.08 to 0.4 g/cm.
  • an apparent density difference of more than 0.8 g/cm or less than 0.05 g/cm between coating layer (III) and (II) the appearance of the creases and the feel and appearance of the artificial leather obtained are not like those of natural leather, and the softness, the draping properties, the
  • the ease of forming creases is expressed by the crease-forming angle described in the following method of measurement. see FIG. 2.
  • crease-forming angle described in the following method of measurement. see FIG. 2.
  • a larger crease-forming angle means it was easier to form creases. Therefore, the satisfactory range of the crease-forming angle of the artificial leather obtained is more than an approximately 40 angle, more satisfactory more than an approximately 60 angle, and the most satisfactory more than approximately an angle.
  • the crease-forming angle of German Box Calf known as the highest class of natural upper leather, is about a 60 angle.
  • the fibrous substrate of this invention is prepared as follows.
  • a well known fibrous web is needle-punched and impregnated with a polymer composition containing a polymer such as polyurethane and adding agent, and then wet-coagulated.
  • a polymer composition containing a polymer such as polyurethane and adding agent
  • It is satisfactory to usefibers of 0.01 to 1.0 denier because the value of flexibility resistance of the artificial leather of this invention using the fibrous substrate, composed of ultra fine fiber bundles as one of the components, in which a denier of each fiber is 0.01 to 1.0, is larger than that of the artificial leather obtained from fibers of ordinary denier.
  • a satisfactory thickness of the fibrous substrate is about 0.3 to 3.0 mm, and more satisfactory about 0.5 to 1.5 mm.
  • the satisfactory range of the viscosities of dimethyl formamide solution with 25 wt% of polyurethane used in the coating layer (I) and the impregnating composition are about 50 to 3,000 poises at 20 C, more satisfactory about to 1,500 poises, and the most satisfactory about 300 to' 800 poises.
  • the satisfactory range of viscosities of dimethyl formamide solution with 25 wt% of polyurethane used in coating layers (II) and (III) are about 200 to 5,000 poises, more satisfactory about 500 to 3,000 poises and the most satisfactory about 800 to 2,000 poises, all measured at 20 C.
  • a satisfactory value of flexibility resistance of the artificial leather of this invention is more than about 10 X 10 times, more satisfactory more than about 15 X 10 times, and the most satisfactory more than about 20 X 10 times.
  • Shoes made of artificial leather having less than 10 X 10 times of flexibility resistance are unsatisfactory, because cracks on the shoe surface arise easily. Therefore the above mentioned range of flexibility resistance is desirable.
  • a satisfactory range of water vapor permeability of the artificial leather of this invention is more than about 3 mg/cm hr., more satisfactory more than about 5 mg/cm hr., and the most satisfactory more than about 8 mg/cm hr. It is unsatisfactory to use artificial leather having less than 3 mg/cm hr. of water vapor permeability, because shoes made from'the artificial leather tendtomoisten the feet in ordinary use.
  • the coating composition (II) for coating layer (ll) is uniformly coated on a release support such as plastic film, glass plate, steel plate, or paper, so as to attain a thickness of about 0.01 to 0.3 mm of the coating layer (ll) consisting of the coating composition (ll).
  • Step (2) The coating composition (III) for coating layer (Ill) is uniformly coated on the coating layer (ll) in Step'(l) so as to attain a thicknessof about 0.1 to 3.0 mm of the coating layer (111) consisting of the coating composition ([11).
  • Step (3) r the non-woven, or woven or knitted fabric is impregnated with an impregnating composition and then'coagulated by immersing in a liquid which is a non-solvent for the polymer.
  • the product of this step is immersed in a solution composed of nonsolvent and solvent for the polymer in the impregnating composition. In this way the wet-treated fibrous substrate is obtained. This is then applied to the'surface of the coating layer (lll) obtained in Step (2), and pressed lightly.
  • Step (4) The material obtained in Step (3 coagulated in a coagulating liquid for a definite time at a definite temperature, to obtain a microporous structure of coating layer (ll) and (lll), and to unite the coating (ll) and (Ill) with the fibrous substrate.
  • Step (5) I v The release support is stripped from the surface of the coating layer (I1), and the solvent which is contained in the coating layer (ll), (Ill) and wet-fibrous substrate is extracted and washed and. then dried.
  • the coating composition (1) for coating layer (l) is coatedon the surface of the coating layer (ll) so as to attain 0.001 to 0.1 mm in thickness of the coating layer (l), and then dried.
  • an artificial leather obtainedbythe following alternative method has no'crease on the surface atall, and the properaties such as the flexibility resistance (3 X times), the scuff resistance (300 g), the heat resistance (105 C), the surface smoothness, the color and luster of the surface and so on, become worse extremely.
  • This alterna tive method is that the coating composition (I) of Step (6), instead of the coating composition (11) of Step (1) is coated on the release support, and then the coating composition (ll) of Step (1) is coated on'the coating layer (l) and then the coating composition (Ill) of Step (2) is coated on this, and then the treatment of Steps 3) to (5) is carried out in order.
  • Step (5) There are the following methods instead of Step (5). Namely, (a) the solvent which is contained in the coating layer (ll), (Ill) and wet-fibrous substrate is extracted and washed, and the release support is stripped from the coating layer (ll), and then dried, and (b) the solvent which is contained in the coating layer (ll), (lll) andwet-fibrous substrate is extracted and washed, and dried, and then the release support is stripped from the coating layer (ll).
  • Said method (a) has a characteristic that the artificial leather is not deformed by heat shrinkage when extracted and washed to C).
  • Said method (b) has a characteristic that the artificial leather is not deformed by heat shrinkage when dried (60 to 180 C) in addition to the above mentioned characteristic in method (a).
  • Step (5) can be preferable industrially to either method (a) or (b), because the extracting and washing times are shortened to less than half of that in (a) or (b), the productive capacity increases more, the equipment is simpler and proper equipment will be able to resolve the problem of shrinkage.
  • the thickness of coating layers This value is measured from a microphotograph of the cross-section of each coating layer.
  • WVP Water vapor permeability
  • This value is measured by the Calcium Chloride-cup method which is defined by Japanese Industrial Standard (.llS) K-6549, which measurement comprises setting a circular sample having an area of 28.3 cm on a measuring cup including 10 g of solid'calcium chloride inside, sealing tightly with melted paraffin which solidifies immediately, and maintaining for 4 hours in an atmosphere of 40 C and 90 i 5 percent of relative humidity.
  • weight of sealed cup after This value is defined as the weight per unit volume (g/cm obtained by measuring the weight of the sam ple having a size of -5 cm X 5 cm with a chemical balance and calculating grams per unit volume of the sample by using the sample size and thickness.
  • the difference of the apparent density (apparent density difference) among layers is obtained as follows.
  • each mono-coating layer is prepared individually from the corresponding composition, corresponding to each layer inthe multicoating layer, and the apparent density of each layer is measured by the above mentioned method and'the apparent density difference is calculated.
  • The, apparent density is the average value of 10 samples.
  • modulus This value is defined as the stress at 20 percent elongation expressed as kg/cm and it may be by a measure of the softness, whose measurement comprises maintaining the sample having a size of 2 cm X 13 cm for at least 24 hours in an atmosphere of 20 C and 65 percent R.l-l., applying the sample to a tensile testing apparatus, measuring at the condition of a pulling speed of 10 cm/min, a chart speed of 10 cm/min (test length of 10 cm and test width of 2 cm) and reading the stress at 20 percent elongation from the load-elongation curve thus obtained on the chart.
  • a dry coagulating coating layer (1) a mixture of 100 parts of DMF solution with wt% polyurethane and 20 parts of carbon black dispersion of 18 percent by weight is coated on a polyethylene terephthalate film at a thickness of 2.0 mm and dried for 1 hour at 100 C. The resulting dry film is cut into pieces (above mentioned size) and the 20 percent modulus is measured under the above conditions. 5.
  • Flexibility resistance (De Mattia Flex Test resistance) This value is defined as flexibility resistance measured by De Mattia Flex Tester whose measurement comprises folding the sample (4 X 10 cm) into two and flexing the folded sample several times in the fingers, as shown in FIG.
  • De Mattia Flex Test resistance is abbreviated as DM re.- sistance.
  • DM resistance is expressed as an average of five samples.
  • Appearance of creases v This value isexpressed by the comparison with the appearance of creases in German Box Calf. This comprises bending the leather in such a way that the top coating is the inside, and evaluating the appearance of creases in comparison with that of German Box Calf by observing the length, the width, the depth and the direction of the creases. The creases of German Box Calf are qualitatively small and relatively shallow, and appear in all directions. If necessary, a photograph of creases may be used as the judgment reference.
  • Scuff (scratch) resistance This value is defined as the lowest load (grams) on the following needle which hurts the surface of a sample (5 X 5 cm) cemented to the regular position of the standard Clemence Scratch Resistance Tester.
  • Part(s) used in the following description means part(s) by weight unless specifically designated otherwise.
  • EXPERIMENTI A. Preparation of non-woven fabric 40 parts of Nylon-6 staple fibers, of 3 denier and having a-length of 51 mm, and 60 parts of polyethylene I terephthalate staple fiber of 5 denier and having a length of 51 mm, were respectively opened and then mixed. The mixed staple fiber was treated in crosslappin'g equipment to obtain a web and then was needle-punched to obtain a non-woven fabric. This nonwoven fabric was heat pressed with a calender roll to obtain a non-woven fabric having a unit area weight of 200 g/m and a thickness of 0.8 mm. B.
  • EXPERIMENT Vl According to Experiment l, 8 kinds of artificial leather were prepared except that in coating composition (ll) and (Ill), 0.01, 0.03, 0.10, 0.50, 2.00, 3.00,
  • W.V.P. (mg lcm. hr.) 5. 5 10. 5 13.0 15. 5 16. 16.0 16.0 1;. ll
  • 20 percent modulus of coating layer (1) was effective to appearance of creases, crease-forming angle, and flexibility resistance of artificial leather as shown in Table 9.
  • from to 100 kg/cm of 20 percent modulus of coating layer (1) was satisfactory, more satisfactory from to 70 kg/cm and the most satisfactory from to 50 kg/cm EXPERIMENT [X With the same conditions as in Experiment I and Experiment I-1 except that coating layer (11); and (111) v, mean particle diameter of inorganic compound particlc.
  • the resulting artificial leather had from 0.00 to 1.00 g/cm of apparent density difference between coating layer (Ill) and (II). Table 10 shows that in order to obtain good artificial leather with satisfactory properties at the same time, it is necessary to make the apparent density difference from 0.05 to 0.80 g/cm,
  • MBA methylene his-aniline I W i V N (EXP. VIII) Hm m w 20% modulus of C.L. (I) and the properties of artificial leather
  • EXPERIMENT x Using the conditions of Table 1 ll eight kinds of artificial leather (from Experiment X-l to X-6, Comparison X-l and Comparison X-2 as shown in Table 11-1 ing layer (ll) and (III) was kept as shown in Table l l-i which is a favorable value according to this invention.
  • Table l l-l shows that it is necessary to make the thickness of coating layer (1) from 0.001 to 0.1 mm.
  • eight kinds of artificial leather from Experiment X-7 to X-l2 and Comparison X-3 to X-4 as shown in Table l l-2) were prepared according to Experiment I and Experiment l-l.
  • Table l l-2 shows that it is necessary to make the thickness of coating layer (ll) from about 0.01 to about 0.30 mm.
  • Table l l-3 Eight kinds of artificial leather (from Experiment X-l3 to X-l8 and Comparison X-5 to X-6 as shown in Table ll-3) were prepared according to Experiment I and Experiment [-1 except that the thickness of coating layer (ill) was changed and that the value of the thickness of coating layer (1) and (11) was kept as shown in Table ll-3, which is a favorable value according to this invention.
  • Table l l-3 shows that it is necessary to make the'thickness of the coating layer (Ill) from about 0.10 to about 3.00 mm.
  • the favorable thickness of fibrous substrate was from about 0.3 to 3.0 mm and that a more favorabie thickness was from about 0.5 to 1.5' mm for shoes, bags, sheets, interior materials, etc), for ease of processing, although the optimum thickness differs according to use. It was also found that the thickness of the fibrous substrate affected the creasefs mi s ns r v s 9 cr ses.. lai ail nr ss tance, softness, appearance and feel, and that the range of the thickness above mentioned gave good results.
  • An artificial leather consisting of coating layer (1), (ill) and fibrous substrate without coating layer (II) was prepared, but flexibility resistance of this artificial leather was very poor (0.2 X 10 times), and shoes made of this artificial leather were so poor that cracks occurred in about one day when the shoes were worn. Also, their scuff resistance was very weak (200 g), and the shoes were easily scratched when worn.
  • poly-tctra-meth an artificial leather was prepared accor ding to Experiment! and coating composition (III). according to Experiment l-l.
  • g PU used in CO3 was choscn.
  • coating compositions (I), (II), (III) and the impregnating composition were prepared.
  • the polymer used for coating compositions (I), (II), (III) and impregnating composition was the same kind as PU as used in Experiment I.
  • artificial leathers were prepared according to Ex periment l and Experiment [-1. As a result it was found that, when the viscosities'mentioned below were used, the resulting artificial leather had a satisfactory appearance of creases, a large crease-forming angle, superiorflexibility resistance, strong scuff resistance, wonderful softness, great repulsive elasticity, etc., all at the same time.
  • the satisfactory extent of the viscosity of the DMF solution with 25 wt% of PU used for the coating layer (I) and'the impregnating composition was from about 50 to 3,000 poises at20 C, more satisfactoryfrom about 100 to 1,500 poises and most satisfactory .from about 300 to800 poises.
  • the satisfactory range of viscosity of the DMF solution with 25 wt% of PU used for the coating layers (II) and (III) was from about 200 to 5,000 poises at 20 C, more satisfactory from about 500 to 3,000 poises, and the most satisfac tory from about 800 to 2,000 poises.
  • coating layers (II) and (III) it is important to obtain a microporous structure by the wet-coagulating method. And it is also important that the state of dispersion of the inorganic compound in the coating composition should be substantially homogeneous. For the reason mentioned above, it is considered that good results were obtained in the range of viscosities mentioned above.
  • EXPERIMENT XIV By making a web of polyethylene terephthalate staple fibers of ultra fine fiber bundle in which each fiber had a denier of 0.08, and needle-punching the web, a nonwoven fabric was made. Artificial leather was prepared according to Experiment I. Coating composition (III) in Experiment H was used as coating composition (Ill).
  • the resulting artificial leather was superior in softness and flexibility resistance X 10 times) and the appearance and feel of this artificial leather were I just the same as that of German Box Calf. The appearance of creases and the crease-forming angle were almost the same as Experiment I. The ease in shoemaking was superior. The shoes from this artificial leather gave no discomfor when worn.
  • tance was from 1,300 to 1,500 g.
  • EXPERIMENT XV The surface of wet-treated fibrous substrate was flattened by the dispersion liquid of poly-ethyl acrylate and water (30:70 by weight), and then on this surface, coating layers (II) and (III) were applied and pressed.
  • artificial leather was prepared according to Experiment I.
  • Coating composition (III) in Experiment l-l was used
  • EXPERIMENT XVI Flattening treatment of surface of the fibrous sub- S a in in n??? is P 9s9a$ 9l Q
  • the surface of wet-treated fibrous substrate in Experiment I was flattened by coating with PU and/or a dispersion liquid composed of alkyl-poly-acylate and water.
  • PU PU
  • a dispersion liquid composed of alkyl-poly-acylate and water.
  • the surface of coatinglayer-(lll)-side of multi-layer material of coating layer (II) and (III) was applied, and pressed lightly, then immersed into water to coagulate. Then, on the surface of coating layer (ll), coating layer (I) was applied.
  • artificial leather was prepared.
  • the artificial leather obtained by the method of (l) and (2) above mentioned had superior flexibility resistance, scuff resistance, and water vapor permeability.
  • the properties of the artificial leather obtained by the method of (3) were as superior as those of l) and (2) except for water vapor permeability.
  • Example H 65 X 10 times 16.0 mg/cm hr. 1800 g Flexibility resistance: Water vapor permeability: Scuff resistance:
  • Artificial leather comprising a fibrous substrate having a thickness of about 0.3 to 3.0 mm, said substrate comprising a fabric impregnated with a polymer, 1 and coating layers (Ill), (11) and (l) adhered in that order to the surface of said substrate,
  • the coating layer (llI) having a thickness of about 0.1 to 3.0 mm, and comprising a wet coagulated polymer composition which contains about 50 to 300 parts by weight of inorganic particles per 100 parts by weight of polymer, said inorganic particles having a mean particle diameter of about 0.03 to 5.0 micron and being essentially insoluble in water, and the polymer in this polymer composition consisting of at least about 60 percent by weight of polyurethane,
  • the coating layer (ll) having a thickness of about 0.01 to 0.3 mm, and comprising a wet coagulated polymer composition which contains about to 50 parts by weight of inorganic particles per 100 parts by weight of polymer, said inorganic particles having a mean particle diameter of about 0.03 to 5.0 micron and being essentially insoluble in water, and the polymer in this polymer composition consisting of at least about 80 percent by weight of polyurethane, and
  • the coating layer (I) having a thickness of about 0.001 to 0.1 mm and having a 20 percent modulus of about to 100 kglcm and comprising a drycoagulated polymer composition, consisting essentially of at least about 80 percent by weight of polyurethane.
  • the thickness of said fibrous substrate is about 0.5 to 1.5 mm
  • the thickness of said coating layer (1) is about 0.003 to 0.05 mm
  • the 20 percent modulus of said coating layer (1) is about to 70 kg/cm
  • the thickness of said coating layer (11) is about 0.03 to 0.25 mm
  • said coating layer (11) contains about 0 to parts by weight of inorganic compound particles per 100 parts by weight of polymer, these inorganic particles having a mean particle diameter of about 0.1 to 3.0 micron, and being essentially insoluble in water
  • the thickness of said coating layer (111) is about 0.3 to 2.0 mm
  • said coating layer (llI) contains about .80 to 200 parts by weight of inorganic compound particles per 100 parts by weight of polymer, and these inorganic compound particles having a mean particle diameter of about 0.1
  • said coating 1a 'ei iiu when. about 120 to 160 parts by weight of inorganic compound particles per 100 parts by weight of polymer, and these inorganic compound particles have a mean particle diameter of about 0.5 to 2.0 micron and are essentially insoluble in water. 4.
  • said polymer contained in said coating layers (1) and (II) is composed of more than wt% of polyurethane and less than 20 wt% of another polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, poly-vinyl acetate, poly-acrylic acid, alkyl-polyacrylate, poly-methacrylic acid, alkylpoly-methacrylate, a copolymer consisting of at least one of the above mentioned polymer segments, and mixtures of the above mentioned polymer, and said polymer contained in said coating layer (111) is composed of more than about 60 percent'by weight of polyurethane and less than about 40 percent by weight of such other polymer.
  • another polymer selected from the group consisting of polyvinyl chloride, polyvinylidene chloride, poly-vinyl acetate, poly-acrylic acid, alkyl-polyacrylate, poly-methacrylic acid, alkylpoly-methacrylate, a copoly
  • the polyurethane contained in said coating layer (1), (11) and (H1) is the reaction product of a polymer diol, diisocyanate and di-amine and/or lower molecular diol, wherein the polymer diol is at least one kind of polymer diol from the group composed of poly-ether-diol, polyester-diol and poly-ether-ester-diol, and the polymer contained in impregnating composition is selected from the group consisting of the polyurethane in this claim, and one kind of other polymer from the group composed of polyvinyl chloride, copolymer of vinyl chloride and vinyl acetate, poly-acrylic acid and its ester, and poly-methacrylic acid and its ester, and a mixture of more than about 50 percent by weight of polyurethane and less than about 50% by weight of such other polymer.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
US00298449A 1972-10-17 1972-10-17 Artificial leather Expired - Lifetime US3841897A (en)

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US00298449A US3841897A (en) 1972-10-17 1972-10-17 Artificial leather
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GB4920572A GB1412261A (en) 1972-10-17 1972-10-25 Simulated leathers
US45191574 US3908060A (en) 1972-10-17 1974-03-18 Artificial leather and method of preparation

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US3922402A (en) * 1973-05-07 1975-11-25 Kuraray Co Production of artificial leather
US3974320A (en) * 1972-08-11 1976-08-10 Akzo N.V. Of Arnhem, Holland Synthetic leather product and method of production
US4018954A (en) * 1969-08-19 1977-04-19 Kuraray Co., Ltd. Sheet material
US4216251A (en) * 1977-09-05 1980-08-05 Kuraray Co., Ltd. Method of producing a leather-like sheet material having a high-quality feeling
EP0523806A1 (en) * 1991-07-15 1993-01-20 Unitika Ltd. Moisture permeable and waterproof coated fabric and method for manufacturing same
ES2162577A1 (es) * 1999-09-16 2001-12-16 Morro Jorge Coll Contrafuerte y tope de la estructura interior de un zapato.
US20030204942A1 (en) * 2002-03-11 2003-11-06 Wang Ching Tang Artificial leather composite reinforced with ultramicrofiber nonwoven fabric
EP1312272A3 (de) * 2001-11-14 2003-12-03 Küsters, Peter Kunststoffmembran, deren Herstellung und Verwendung
US20040013883A1 (en) * 2000-10-19 2004-01-22 Mario Polegato Moretti Waterproof breathable layered article with high mechanical strength
US20040191412A1 (en) * 2003-03-11 2004-09-30 San Fang Chemical Industry Co., Ltd. Process for making ultra micro fiber artificial leather
US20040237221A1 (en) * 2001-12-17 2004-12-02 Rhee Jin Sup Polyurethane artificial leather and transfer printing method thereof
US20050100710A1 (en) * 2003-11-10 2005-05-12 San Fang Chemical Industry Co., Ltd. Flameproof environmentally friendly artificial leather and process for making the same
US20050170168A1 (en) * 2003-12-31 2005-08-04 San Fang Chemical Industry Co., Ltd. Sheet made of high molecular material and method for making same
US20050181190A1 (en) * 2003-12-31 2005-08-18 San Fang Chemical Industry Co., Ltd Sheet made of high molecular material and method for making same
US20050260416A1 (en) * 2003-01-13 2005-11-24 San Fang Chemical Industry Co., Ltd. Environmental friendly artificial leather product and method for producing same
US20060046597A1 (en) * 2004-08-24 2006-03-02 San Fang Chemical Industry Co., Ltd. Permeable artificial leather with realistic feeling and method for making the same
US20060057432A1 (en) * 2004-09-16 2006-03-16 San Fang Chemical Industry Co., Ltd. Elastic artificial leather
US20060147642A1 (en) * 2004-05-03 2006-07-06 San Fang Chemical Industry Co. Ltd. Method for producing artificial leather
US20060160449A1 (en) * 2005-01-19 2006-07-20 San Fang Chemical Industry Co., Ltd. Moisture-absorbing, quick drying, thermally insulating, elastic laminate and method for making the same
US20060218729A1 (en) * 2005-03-30 2006-10-05 San Fang Chemical Industry Co., Ltd. Method for making environment-friendly artificial leather from ultra micro fiber without solvent treatment
US20060249244A1 (en) * 2004-01-09 2006-11-09 San Fang Chemical Industry Co. Ltd. Method for producing environmental friendly artificial leather product
US20060263601A1 (en) * 2005-05-17 2006-11-23 San Fang Chemical Industry Co., Ltd. Substrate of artificial leather including ultrafine fibers and methods for making the same
US20060270329A1 (en) * 2005-05-27 2006-11-30 San Fang Chemical Industry Co., Ltd. Ultra fine fiber polishing pad and method for manufacturing the same
US20060272770A1 (en) * 2004-08-24 2006-12-07 San Fang Chemical Industry Co., Ltd. Method for making artificial leather with superficial texture
US20070155268A1 (en) * 2005-12-30 2007-07-05 San Fang Chemical Industry Co., Ltd. Polishing pad and method for manufacturing the polishing pad
US20070207687A1 (en) * 2004-05-03 2007-09-06 San Fang Chemical Industry Co., Ltd. Method for producing artificial leather
US20070218791A1 (en) * 2006-03-15 2007-09-20 San Fang Chemical Industry Co., Ltd. Artificial leather with even imprinted texture and method for making the same
US20070231546A1 (en) * 2006-03-31 2007-10-04 Jusong Xia Synthetic leather articles and methods for producing the same
US20070231547A1 (en) * 2002-08-22 2007-10-04 Kurray Co., Ltd. Grain-Finished Artificial Leathers
US20080095945A1 (en) * 2004-12-30 2008-04-24 Ching-Tang Wang Method for Making Macromolecular Laminate
US20080113198A1 (en) * 2006-11-10 2008-05-15 Jusong Xia Leather articles and methods for producing the same
US20080138271A1 (en) * 2006-12-07 2008-06-12 Kuo-Kuang Cheng Method for Making Ultra-Fine Carbon Fibers and Activated Ultra-Fine Carbon Fibers
US20080149264A1 (en) * 2004-11-09 2008-06-26 Chung-Chih Feng Method for Making Flameproof Environmentally Friendly Artificial Leather
US20080187715A1 (en) * 2005-08-08 2008-08-07 Ko-Feng Wang Elastic Laminate and Method for Making The Same
US20080220701A1 (en) * 2005-12-30 2008-09-11 Chung-Ching Feng Polishing Pad and Method for Making the Same
US20080261052A1 (en) * 2006-03-31 2008-10-23 Jusong Xia Coated substrates and polymer dispersions suitable for use in making the same
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US20100330334A1 (en) * 2009-06-24 2010-12-30 San Fang Chemical Industry Co., Ltd. Artificial leather and method for manufacturing the same
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US20110111657A1 (en) * 2006-03-31 2011-05-12 Jusong Xia Coated substrates and polymer dispersions suitable for use in making the same
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US20180258584A1 (en) * 2017-03-09 2018-09-13 Hyundai Motor Company High density artificial leather having excellent surface touch and method of manufacturing the same
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US20200268077A1 (en) * 2019-02-25 2020-08-27 Rawlings Sporting Goods Company, Inc. Glove with structural finger reinforcements
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US5393600A (en) * 1993-03-25 1995-02-28 Kuraray Co., Ltd. Highly flexible leather-like sheet material and process for producing the same

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US4018954A (en) * 1969-08-19 1977-04-19 Kuraray Co., Ltd. Sheet material
US3974320A (en) * 1972-08-11 1976-08-10 Akzo N.V. Of Arnhem, Holland Synthetic leather product and method of production
US3922402A (en) * 1973-05-07 1975-11-25 Kuraray Co Production of artificial leather
US4216251A (en) * 1977-09-05 1980-08-05 Kuraray Co., Ltd. Method of producing a leather-like sheet material having a high-quality feeling
EP0523806A1 (en) * 1991-07-15 1993-01-20 Unitika Ltd. Moisture permeable and waterproof coated fabric and method for manufacturing same
ES2162577A1 (es) * 1999-09-16 2001-12-16 Morro Jorge Coll Contrafuerte y tope de la estructura interior de un zapato.
US20040013883A1 (en) * 2000-10-19 2004-01-22 Mario Polegato Moretti Waterproof breathable layered article with high mechanical strength
EP1312272A3 (de) * 2001-11-14 2003-12-03 Küsters, Peter Kunststoffmembran, deren Herstellung und Verwendung
US20040237221A1 (en) * 2001-12-17 2004-12-02 Rhee Jin Sup Polyurethane artificial leather and transfer printing method thereof
US20030204942A1 (en) * 2002-03-11 2003-11-06 Wang Ching Tang Artificial leather composite reinforced with ultramicrofiber nonwoven fabric
US7132024B2 (en) * 2002-03-11 2006-11-07 San Fang Chemical Industry Company, Ltd. Artificial leather composite reinforced with ultramicrofiber nonwoven fabric
US7442429B2 (en) * 2002-08-22 2008-10-28 Kuraray Co., Ltd. Grain-finished artificial leathers
US20070231547A1 (en) * 2002-08-22 2007-10-04 Kurray Co., Ltd. Grain-Finished Artificial Leathers
US20050260416A1 (en) * 2003-01-13 2005-11-24 San Fang Chemical Industry Co., Ltd. Environmental friendly artificial leather product and method for producing same
US20040191412A1 (en) * 2003-03-11 2004-09-30 San Fang Chemical Industry Co., Ltd. Process for making ultra micro fiber artificial leather
US20050100710A1 (en) * 2003-11-10 2005-05-12 San Fang Chemical Industry Co., Ltd. Flameproof environmentally friendly artificial leather and process for making the same
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US20060160449A1 (en) * 2005-01-19 2006-07-20 San Fang Chemical Industry Co., Ltd. Moisture-absorbing, quick drying, thermally insulating, elastic laminate and method for making the same
US20060218729A1 (en) * 2005-03-30 2006-10-05 San Fang Chemical Industry Co., Ltd. Method for making environment-friendly artificial leather from ultra micro fiber without solvent treatment
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US20070231546A1 (en) * 2006-03-31 2007-10-04 Jusong Xia Synthetic leather articles and methods for producing the same
US20080113198A1 (en) * 2006-11-10 2008-05-15 Jusong Xia Leather articles and methods for producing the same
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CN110042675B (zh) * 2019-04-08 2021-05-18 温州大学 一种超纤贝斯全水性后处理方法
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