Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • 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
  • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • 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
• • 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.]
  • Y10T428/24058—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in respective layers or components in angular relation
• • 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.]
  • Y10T428/24132—Structurally defined web or sheet [e.g., overall dimension, etc.] including grain, strips, or filamentary elements in different layers or components parallel
• • 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.]
  • Y10T428/24942—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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
  • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
• • 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
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/266—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension of base or substrate
• • 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
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
  • Y10T442/647—Including a foamed layer or component

Definitions

• the present invention provides artificial leather with silver tone, which has functionalities such as air permeability and moisture permeability, and has improved conventional surface defects such as surface smoothness, antifouling property, and abrasion resistance.
• secondary products such as shoes, gloves, chairs, and clothes, at least partially including such artificial leather with silver tone.
• artificial leather composed of fibrous material and polymer elastic material has been widely used as a substitute for leather in applications such as shoe upper materials, shoe accessory materials, and clothing materials. It is a material that cannot be obtained.
• These artificial leathers are roughly classified into a suede type, a nubuck type and a silver type according to the surface morphology. Among them, suede type and nubuck type can be obtained with high air permeability and high moisture permeability.However, silver type is made of non-porous finishing synthetic resin, At present, moisture permeability is not satisfactory.
• artificial leather with silver which is used for shoe upper materials and clothing, has a large “humidity” when worn, and improvement from the market is desired.
• artificial leather has been proposed in which a finished polyurethane film is formed on the surface of a base material composed of a fibrous material and a polymer elastic material, and the property of a discontinuous film is used. It has the drawbacks that it is too large to be stained and that the fiber skin cannot be concealed and a smooth and elegant appearance cannot be obtained, or that there is no porous polyurethane layer, resulting in poor abrasion resistance.
• Japanese Patent Application Laid-Open No. 59-1161679 discloses that a polymer solution is applied to the surface of a substrate composed of an arrowhead fiber or a fiber and a polymer, and the polymer solution is applied.
• a method of forming a silver surface having pores by slightly drying, pressing a releasable support having a fine uneven surface, pressing the support, and then peeling the support.
• the silver surface layer is formed directly on the fibrous substrate, the fiber skin of the substrate is likely to appear on the silver surface during elongation. It has disadvantages such as inferior wear and poor wear strength.
• Japanese Patent Application Laid-Open No. Hei 7-79643 discloses that a finished polyurethane film is formed from a W / 0 emulsion as a porous film on a woven fabric substrate to improve air permeability and moisture permeability.
• a method for producing artificial leather having the same has been proposed. However, this method does. Since the outermost finished polyurethane coating is porous, its mechanical strength is lower than that of non-porous polyurethane coating, and its wear resistance is defective. The precondition is that open pores are formed stably on the surface of the wet porous polyurethane layer, but this method is industrially poor in stability.
• JP-A-3-140320 discloses that a urethane polyamino acid is formed on a fiber assembly base material as a porous finishing film by using a phase-separating coagulation nucleating agent in combination with a gas-permeable material.
• a method for producing artificial leather has been proposed.
• this method also has the disadvantage that the mechanical strength is weaker than the non-porous polyurethane film, and the abrasion resistance is defective, because the finished polyurethane film on the outermost surface is porous as described above.
• problems such as difficulty in stably forming open pores on the surface of the wet porous polyurethane layer.
• the urethane polyamino acid is priced However, it is disadvantageous in terms of economy.
• An object of the present invention is to provide a silvery tone which has a low stuffiness J when worn or used, is resistant to dirt, has a smooth and elegant surface appearance, and has good abrasion resistance. It is to provide artificial leather and its secondary products at low cost.
• the present invention has, on one surface, a substrate made of a gas-permeable sheet-like fiber aggregate and a communicating micropore inside the substrate fixed to at least one surface of the substrate, and an open hole on the surface.
• a substrate made of a gas-permeable sheet-like fiber aggregate and a communicating micropore inside the substrate fixed to at least one surface of the substrate, and an open hole on the surface.
• a non-porous polyurethane film is further formed on the surface of the porous polyurethane layer having communicating micropores therein;
• the non-porous polyurethane coating extends along the inner wall of each open hole without substantially occluding the space in the non-obstructed open hole. As a result, a narrow squeezing open hole is formed.
• a sports shoe or other shoe in which an upper portion is made of the above-mentioned artificial leather with silver, a glove whose main body portion is made of the above-described artificial leather, and a seat.
• At least one surface of a substrate made of a gas-permeable sheet-like fiber aggregate has communicating micropores therein, and has substantially no open pores on the surface.
• a porous polyurethane layer is fixedly formed, and the surface of the porous polyurethane layer having communicating micropores therein is coated on the surface of the polyurethane and the good solvent, the poor solvent, the mixed solvent of the good solvent and the poor solvent, or
• a mixture of a solvent and a non-solvent is applied by applying a mixture of any one of the solvents in a number of scattered spots to generate a large number of open pores on the surface, and then applying a finishing polyurethane to the surface.
• a method for producing artificial leather with silver characterized in that a non-porous polyurethane coating is formed on the entire surface of a porous polyurethane layer.
• the nonporous polyurethane film is formed on the entire surface of the porous polyurethane layer as described above, and the open hole is closed along the inner wall surface of the open hole. Without this, the non-porous polyurethane coating is extended, thereby forming a squeezed open hole.
• FIG. 1 is an enlarged cross-sectional view showing an example of a non-blocking open pore forming portion present in a porous polyurethane layer having communicating micropores therein and a nonporous polyurethane film.
• Examples of the sheet-like fiber aggregate constituting the artificial leather with tone of the present invention include a conventionally known woven fabric, knitted fabric, and nonwoven fabric made of natural fibers, regenerated fibers, and synthetic fibers.
• a fiber aggregate made of fibers having a high hygroscopic property in order to give a sweat-absorbing property from the back side. Therefore, rayon fiber with high hygroscopicity is suitable for use.
• the physical strength of the sheet-like aggregate for example, the physical or physical properties of polyester fiber or polyamide fiber such as polyethylene terephthalate, or a mixture of polyester fiber and polyamide fiber, for example. Fibers with high strength are preferred. It is also preferable to use these high-strength fibers and rayon fibers in combination.
• a nonwoven fabric is preferable.
• the base material used in the present invention is composed of a sheet-like fiber aggregate alone or a sheet-like fiber aggregate and an elastic polymer.
• the polymer elastic body include polymer elastic bodies that are conventionally used as a substitute for leather, such as polyurethane, polyurea, polyurethane urethane, styrene-butadiene rubber, and acryl-tri-butadiene rubber. No. These are preferably impregnated into the sheet-like fiber aggregate as an aqueous emulsion or a solvent solution, and then coagulated to form a base material composed of the fiber aggregate and a high molecular elastic material.
• the thickness of the base material is preferably in the range of 0.3 to 2.0 with a bulk of 0.2 to 0.6 g / cm 3 .
• a porous polyurethane layer having fine pores therein is formed on at least one surface of the above-mentioned sheet-like fiber aggregate or a substrate comprising the sheet-like fiber aggregate and a polymer elastic body.
• the polyurethane for forming this layer all known polyurethanes can be applied, and any of the conventionally known formation methods can be applied. For example, an organic solvent solution of polyurethane is coated on one side of a sheet-like fiber aggregate or a substrate composed of a textile material and a polymer elastic body, and then the polyurethane is dissolved in a non-solvent of polyurethane.
• Coagulation in a coagulation bath that is miscible with the organic solvent used, or a W-type emulsion, in which water is finely dispersed in an organic solvent solution or dispersion of polyurethane, in the form of sheet fibers There is a method of coating one side of a base material composed of a body or a sheet-like fiber aggregate and a polymer elastic body, and then selectively evaporating an organic solvent to solidify the polyurethane.
• the thickness of the porous polyurethane layer having the internal fine pores is set to 0.03 mn! In order to obtain abrasion resistance, surface smoothness, cushioning property, and a sense of volume. 00.6 mm is preferable, and 0.1 to 0.2 mm is more preferable. If the thickness is less than 0.03 mm, it is not preferable because the texture of the fiber aggregate appears on the surface and it is difficult to obtain a smooth feeling on the surface. On the other hand, when the thickness exceeds 0.6, it is not preferable in that rubber-like artificial leather is produced and productivity is reduced.
• the porous polyurethane layer having communicating micropores inside must be continuous porous. No. In other words, the communicating porous polyurethane layer needs to have air permeability secured by the communicating holes from the surface of the fiber aggregate or the base material side composed of the fiber aggregate and the polymer elastic body to the exposed surface. .
• the open pores are formed by the solvent when the finished polyurethane film is formed. It is either melted and closed, or concealed by the finished polyurethane and loses its breathability.
• the point of the method for producing the artificial leather of the present invention is to apply the finished polyurethane when forming the finished polyurethane film so that an open hole having an appropriate diameter that does not result in loss of air permeability is finally formed.
• an object is to make open pores having an appropriate diameter appear on the surface of the porous polyurethane layer.
• polyurethane and its good solvent, poor solvent, mixed solvent of good and poor solvents, or polyurethane on the surface of the porous polyurethane layer Apply a mixture of a good solvent and a non-solvent mixed solvent in a number of scattered spots.
• a good solvent for polyurethane means a solvent capable of dissolving the polyurethane actually used.
• the good solvent is polyurethane.
• examples include polar solvents such as methylformamide, tetrahydrofuran, and dioxane.
• the poor solvent for polyurethane is a solvent that does not dissolve the actually used polyurethane but can swell.
• ketones such as methylethyl ketone, alcohols such as isopropyl alcohol, and toluene.
• aromatic solvents such as ethylene.
• the non-solvent for polyurethane is one that does not dissolve or swell polyurethane actually used, and is typically water.
• the solubility in the actually used polyurethane can be adjusted, and an appropriate open pore can be developed.
• an open hole is once generated, but the open hole is closed again in the process of evaporating and drying the solvent due to the excessively high solubility.
• a solvent having too low solubility is used, no open pores are developed.
• a gravure mesh roll may be used as a means for applying an appropriately selected solvent to the surface of the porous polyurethane layer in a number of scattered points.
• the size of the mesh of the gravure mesh roll greatly affects the size of the diameter of the open hole formed.
• the use of a finer mesh roll gives a relatively small open hole
• the use of a coarser mesh roll gives a relatively large open hole. Is preferably in the range of generally 70 to 200 mesh.
• the application pressure also depends on the diameter of the open hole formed. Affects the size of That is, if the application pressure is large, the obtained open hole has a large diameter, and if the application pressure is small, the obtained open hole has a small diameter.
• the application pressure of the gravure mesh mouth is preferably in the range of 0.1 to 10 kg / cm 2 .
• the surface of the communicating porous polyurethane layer is preferably 5 to 40 m, more preferably.
• an open pore of 10 m to 30 um is developed.
• the finished polyurethane film is applied to the surface by applying a finishing polyurethane to the entire surface of the communicating porous polyurethane layer. Formed. Some of the open pores formed on the surface of the communicating porous polyurethane layer are closed by the finished polyurethane coating, but the rest is not closed and maintains the state of the open pores. It is important that at least 70% of the non-closed open holes have a diameter of 1 m to 25 m. If the proportion of non-closed open pores whose diameter is less than 1 zm is too large, the air permeability and moisture permeability are too small, and the stuffiness will be increased. In addition, when the ratio of those having a diameter exceeding 25 / m is large, dirt easily enters the open holes, making it difficult to obtain a smooth and elegant surface appearance.
• the non-porous polyurethane film extends along the inner wall of each open hole without substantially closing the space, thereby forming a squeezed open hole.
• Figure 1 shows a state in which such a squeeze opening is formed.
• the communication micropore 2 On the surface of the porous urethane layer 1 (thickness d 2 ), open pores 3 having a diameter are formed, and a non-porous polyurethane film 4 (formed on the porous polyurethane ⁇ 1).
• the thickness d 3 extends from the shoulder of the hole wall of the opening 3 to the inside along the inner wall over a slight length inward without substantially blocking the space of the opening 3.
• a squeeze opening having a diameter of ⁇ 2 is formed.
• Such narrow opening holes are formed, not only the antifouling property and the surface smoothness are improved, but also the abrasion resistance and the durability are remarkably improved.
• Such a narrow opening hole may be appropriately selected by selecting the type of solvent used for preparing the solution and the degree of solution of the solution when applying the polyurethane solution.
• the degree of variation of the polyurethane solution that forms the non-porous polyurethane film has an important effect on the coating amount on the pore wall and the coating depth on the communicating porous polyurethane layer.
• the above-mentioned narrowed open pores can be formed sufficiently with a viscosity of the paint of 80 cm to 200 cm, preferably 10 cm to 140 cm.
• the type of the organic solvent used in the paint for forming the non-porous polyurethane film has a great influence on the pore size of the finally formed open pores.
• the solubility is high in the polyurethane forming the communicating porous layer, the pore wall of the open pore formed in advance on the surface of the communicating porous polyurethane layer is dissolved to reduce the pore diameter. Because it will. The smaller the solubility was, the more it was expressed on the surface of the communicating porous polyurethane layer. The diameter of the open hole can be maintained.
• the organic solvent used as the coating material it is preferable to use a mixed solvent of a solvent having high solubility and a solvent having low solubility in polyurethane forming the communicating porous polyurethane layer.
• the finish nonporous polyurethane coating is required. After formation, the pore diameter is slightly smaller, so the diameter of the open pores on the surface of the communicating porous polyurethane layer before the formation of the polyurethane coating should be between 5 m and 40 m. It turns out that.
• a conventional application method can be adopted, but a method using a gravure coater, a doctor knife coater or the like is preferable.
• the amount of application is in the range of the conventional artificial leather finish coating, that is, 3 g Zm 2 to 20 g / m 2 as solid content, and preferably 5 g Zm 2 to 10 g / m 2 .
• the thickness of the finished non-porous polyurethane film is preferably in the range of 0.01 to 0.02 mm.
• the thickness of the porous polyurethane layer having communicating micropores inside (d 2) and the thickness of the non-porous polyurethane layer (d 3 ) are determined by bending, etc. In order to maintain the balance between the representative hand and the additive properties, it is preferable to satisfy the following relationships (1) and (2). d!
• Auxiliaries having various functions can be mixed into the finished nonporous polyurethane film depending on the use of the artificial leather.
• it can be colored with pigments, dyes, etc. to enhance the costume.
• the artificial leather with silver of the present invention having an open hole has a communication hole extending from the front surface to the back surface, and is breathable, so that when used for shoe upper materials, clothing, etc. It is important to add a water repellent to the finished polyurethane film to impart water repellency, since water may enter. Permanent water repellency can be imparted by using a fluorine-modified polyurethane as a finished polyurethane coating.
• examples of the water repellent include a urethane-modified fluorine-based water repellent excellent in compatibility with polyurethane [Chris Nihon Chemical Industries Co., Ltd., Chris Bon Sister FX-3].
• examples of the fluorine-modified polyurethane include Resoids FF4110 and FF4115 manufactured by Dainichi Seika Kogyo Co., Ltd.
• silicone-modified polyurethane can be used as a water repellent.
• silicone-modified polyurethane can be used as a water repellent.
• it can be distinguished by adding an antioxidant, an antifouling agent, an ultraviolet absorber, etc. to the finished polyurethane film.
• poly urethane Is concerned about discoloration since grain-finished artificial leather of the present invention, which is breathable, and NO x gases such also easily pass structure, poly urethane Is concerned about discoloration.
• the polyurethane constituting the communicating porous polyurethane is generally a polyurethane synthesized from an aromatic disodium.
• the polyurethane used for the finished polyurethane coating is polyurethane with little discoloration, for example, polyurethane synthesized from an aliphatic disodium salt such as 1,6-hexanediisocyanate, In some cases, polyurethanes synthesized from alicyclic diisocynates such as isophorone diisocynate and 4,4'-methylenebis (cyclohexyl succinate) are preferred. In a preferred embodiment of the present invention, since the polyurethane constituting the finished polyurethane film covers the pore walls of the open pores formed by the communicating porous polyurethane layer more deeply, it is more effective in preventing discoloration. Will work.
• various patterns can be usually applied with an embossed knurl as in the production of artificial leather.
• the embossing process can be performed before or after the open pore forming treatment, after forming the finished polyurethane film, or even during the process.
• care must be taken because the open holes may be melted by heat and become smaller.
• the treatment is performed before the open pore development treatment, the density of the dense portion on the surface of the communicating porous polyurethane layer is further increased, and the open pore development treatment may become difficult. Must.
• Open hole number formed on the surface of the grain-finished artificial leather of the present invention preferred properly is 1 cm 2 per 1 0 0-3, 0 0 0, 5 0 0 per 1 cm 2 is properly more preferred ⁇ 3,000. Since the air permeability is determined by the size and number of open holes, the number should be large if the diameter is small, and small if the open hole is large. However, since the moisture permeability largely depends on the number of open holes, the number of open holes generally needs to be 100 or more per 1 cm 2 . If the number of open holes is too small, it becomes difficult to obtain a desired moisture permeability.
• the area of the opening formed by the open holes is preferably 1% or less, more preferably 0.1% to 0.3% of the entire area. If it exceeds 1%, it is not preferable because the wear resistance and the antifouling property are extremely reduced regardless of the size and number of the open pores.
• Silver-finished artificial leather of the present invention is properly preferred ventilation of 0.5 Li Tsu torr Z cm 2 ⁇ hr ⁇ 3 5 Li Tsu torr Z cm 2 ⁇ hr, it is properly more preferred 2 liters / cm 2 iir ⁇ 9 liters cm 2 'hr, preferably 2.0 mg / cm 2 ' hr SO mg / cm 2 hr, more preferably 8 mg / cm 2 ⁇ hr to 14 mg / cm 2 ⁇ hr. If the air permeability and moisture permeability are too low, when used for shoe materials, clothing, etc., there is no difference compared to conventional artificial leather, and stuffiness is felt.
• the above-described air permeability and moisture permeability are satisfied. It may not be possible. For example, if a solid film of a polymer elastic body is formed on the back surface of the base material, it will hinder air permeability and moisture permeability. Therefore, the formation of such a solid film should be avoided.
• a unit of liter / cm 2 'hrJ was calculated from the time required for 50 cc of air to pass, measured using a gauze densomme overnight. It is a value converted to.
• Tobacco ash (mild seven) is ground in a mortar and rubbed on the artificial leather sample with the middle finger clockwise 25 times with the middle finger and 25 times with the left hand so as to draw a circle with a diameter of 36. Then, it was wiped off with absorbent cotton. The dirt on the sample is expressed as grades 1 to 5, with 5 ⁇ being clean.
• a mixture of methyl ethyl ketone (40%) and dimethyl formamide (60%) was applied to the surface of the porous polyurethane layer of the substrate 1 using a gravure coater (using a 110 mesh roll) at 4 kg / cm. Apply under a pressure of 2 and dry. Observation of the surface of the porous polyurethane layer of the obtained substrate 11 with a scanning electron microscope revealed that an infinite number of open pores of about 30 zm were formed. Formation of finish polyurethane coating
• Coating and drying were repeated three times with a gravure coater (using 110 mesh rolls) on the surface of the porous polyurethane layer of the substrate that had been subjected to the open pore development treatment, using the paint 11 prepared with the following composition.
• a hot embossing roll was used to pattern the pores, and the surface was further coated with a paint 12 having the following composition using a gravure applicator (using a 110-mesh roll) and dried to obtain artificial leather 1-1. .
• Crisbon NY320 (Dainippon Ink & Chemicals) 100 parts Howlack A5303 (Dainippon Ink & Chemicals) 30 parts Howlack A1 008 Matt (Dainippon Ink & Chemicals)
• the obtained artificial leather 1 has a white surface, and the surface has an open hole with a diameter of about 13 m. walls about 1 7 0 0 m / cm 2 present in a state which is covered with paint one 1 and coating one 2, whole area of the opening It was equivalent to 0.23% of the area. Both the air permeability and the moisture permeability were superior to those of the conventional artificial leather with silver tone, and were less likely to be stained. Table 1 shows the characteristic values of the obtained artificial leather 1-1.
• Non-woven fabric consisting of a blend of 75% polyester fiber and 25% rayon fiber consisting of split fibers that are alternately adjacent to polyester and 6-nylon (weight: 300 g / m thickness) (1.3 mm) 13% concentration of polyesternopolyether-based polyurethane
• the surface of the porous poly urethane layer of the substrate one 2, Mechiruechiru Ke tons 3 0% and dimethylformamide A mi de 70% of the mixture graphene via coating machine (1 1 0 rolls used in mesh) in a 3 KgZcm 2 Coated under pressure and dried. Observation of the surface of the porous polyester layer of the obtained base material 12 with a scanning electron microscope revealed that about 25 ⁇ 1 open holes were formed innumerably. Formation of finished polyurethane film
• the obtained artificial leather 1-2 has a white surface, an open hole with a diameter of about 10 zm on the surface, and the walls of the holes are paint-3 and paint-4. There were about 2,200 particles / cm 2 in a state covered with, and the area of the open part was equivalent to 0.17% of the total area. Both the air permeability and the moisture permeability were superior to those of conventional artificial leather with silver tone, and they were resistant to dirt and had high water repellency. Table 1 shows the characteristic values of the obtained artificial leather-2.
• a mixture of 30% of methylethylketone and 70% of dimethylformamide was coated on the surface of the porous polyurethane layer of the substrate-2 before the open pore development treatment prepared in Example 2 with a gravure coating machine (200%). (With the use of a brush roll) at a pressure of 5 kg / cm 2 and dried. Observation of the surface of the porous polyurethane layer of the obtained base material 13 with a scanning electron microscope revealed that about 15 m of open pores were formed innumerably.
• the coating material 13 prepared in Example 2 was applied to the surface of the porous polyurethane layer of the substrate having been subjected to the above-mentioned open pore development treatment using a gravure coating machine (using a 200-mesh roll), and drying was repeated three times.
• the surface is then coated with a paint-5 of the following composition using a gravure coater (using a 200-mesh roll) and dried twice, and then patterned with a heated embossing roll in a bloody tone. Get 3 Was.
• Laseroid LU41 80SF (manufactured by Dainichi Seika Kogyo Co., Ltd.) 100 copies
• Crisbon Assist Yuichi FX3 water repellent (Dainippon Inki Chemical Industry Co., Ltd.) 2 parts
• the resulting artificial leather—3 has a white surface and an open hole with a diameter of about 7 m on the surface. wall about 3, 1 0 0 in a state covered with paint one 3 and coating one 5 Z cm 2 exists, the area of the opening portion was equivalent to 0.1 2% of the total area.
• Both the air permeability and the moisture permeability were superior to those of conventional artificial leather with silver tone, and they were resistant to dirt and had high water repellency.
• Table 1 shows the characteristic values of the obtained artificial leather-3.
• the coating material 6 having the following composition was coated on the surface of the porous polyurethane layer of the substrate 2 having been subjected to the open pore development treatment prepared in Example 2 with a gravure coating machine (using a 110 mesh roll). The coating and drying were repeated twice, and then the coating 14 prepared in Example 2 was applied to the surface with a gravure coating machine (using a 110-mesh roll), dried twice, and further heated with an embossing roll. A pattern was applied to the blood tone to obtain artificial leather-4. '
• the paint 11 prepared in Example 1 was applied to the surface of the porous polyurethane layer of the substrate -1 (without open pore development treatment) prepared in Example 1 by a gravure coating machine (roll of 110 mesh). The application and drying were repeated three times, and then the pattern was applied in a pore-like manner with a heated embossing roll. Further, the paint 1-2 prepared in Example 1 was coated on the surface with a gravure coating machine (110) This was applied using a mesh roll) and dried to obtain artificial leather 15. The obtained artificial leather has a white surface, which is apparently the same as the artificial leather obtained in Example 1, but when observed by a scanning electron microscope, no open holes are found and there is no air permeability at all. It had the same moisture permeability as conventional artificial leather. Table 1 shows the characteristic values of the obtained artificial leather-5. Comparative Example 2
• the surface of the artificial leather-5 created in Comparative Example 1 was mechanically treated with a needle to provide nine holes per cm 2 .
• the diameter of the open holes on the surface was 150 m, and although it had air permeability, its moisture permeability was comparable to that of conventional human leather. When it was actually molded into shoes and worn, it was easy to get dirty, and even after washing, the dirt entered the open holes, and dirt hardly fell off.
• Table 1 shows the characteristic values of artificial leather 16 provided with this needle hole.
• Thickness 1.0 Using a nonwoven fabric made of a hidden polyester fabric, the same impregnated substrate as in Example 1 was applied to one side of the impregnated substrate obtained by the same operation as in Example 1. created the 3 - After Koti ring in dimethylformamide ⁇ Mi de solution 9 0 g basis weight of Z ni 2, immersion coagulation, washed with water and dried to a substrate. The resulting substrate had a textile layer thickness of 1.0 mm and a porous polyurethane layer thickness of 38 m. The surface of the substrate 13 was subjected to open pore development treatment, formation of a finished polyurethane film, and patterning in the same manner as in Example 1 to obtain artificial leather-7.
• a mixture of 30% of methylethyl ketone and 70% of dimethylformamide was applied to the surface of the porous polyurethane layer of the substrate 1-1 (without open pore development treatment) prepared in Example 1 by a gravure coating machine (7).
• the coating was dried at a pressure of 4 kg / cm 2 using a 0-mesh roll.
• a finished polyurethane film was formed and patterned by the same operation as in Example 1 to obtain artificial leather 18.
• the air permeability and moisture permeability were both superior to those of conventional artificial leather.However, dirt easily adhered to them. It was easy to clean, and the dirt did not completely come off because the dirt had entered the open holes even after washing. In addition, it was easily worn, the diameter of the open hole became larger, and dirt became more intense with the wearing time.
• a mixture of 50% methylethylketone and 50% dimethylformamide was applied to the surface of the porous polyurethane layer of the substrate-1 (without open pore development treatment) prepared in Example 1 by a gravure coating machine. (Use a 200-mesh roll with a mesh portion of 60%), and dried by applying a pressure of 4 kg Z cm 2 . Get Observation of the surface of the obtained substrate 11 with a scanning electron microscope revealed that an infinite number of open holes of about 15 m were formed. On the surface of the substrate 11 which had been subjected to the open pore development treatment, a finished polyurethane film was formed and patterned by the same operations as in Example 1 to obtain artificial leather-9.
• a mixture of 70% of methylethylketone and 30% of dimethylformamide was applied to the surface of the porous polyurethane layer of the substrate-1 (without open pore development treatment) prepared in Example 1 by a gravure coating machine (2 A roll of 00 mesh and a mesh portion of 60% was used) and dried at a pressure of 2 kg Z cm 2 . Observation of the surface of the obtained base body 11 with a scanning electron microscope revealed that open holes of about 9 m were formed sporadically. On the surface of the substrate 1 having been subjected to the open pore development treatment, a finished polyurethane film was formed and patterned by the same operations as in Example 1 to obtain artificial leather 10.
• the resulting artificial leather-10 has about 150 open pores with a diameter of about 3 m on the surface, and the area of the open area is equivalent to 0.01% of the total area. there were. As shown in Table 1, the air permeability and moisture permeability were 0.1 liter / cm 2 ⁇ hr and 3.7 mg / cm 2 'hr, respectively. When this artificial leather 10 was molded into shoes and worn, a “feel of stuffiness” was felt. No difference was felt.
• the artificial leather produced in each of the above Examples and Comparative Examples was used as an upper to make shoes with a tennis shoe design to obtain shoes.
• shoes 1 1 made with artificial leather 1-1 of Example 1 and shoes 2 made with artificial leather 1 of Example 2 and shoes made with artificial leather 15 of Comparative Example 1 Wear the shoes 1-6 made of the artificial leather 1-6 of the zoom 5 and the comparative example 2 on the right foot and the left foot, respectively, and jog a distance of 3 km.
• the humidity was measured. When this test was performed by 10 people and the average value was compared, the temperature and humidity in the shoes of Examples 1 and 2 were lower than those of the shoes of Comparative Examples 1 and 2. At 1 ° C and 5-7% RH, respectively, the wearer could fully feel the difference in the stuffiness. Table 2 shows the results of this test.
• the silver-toned artificial leather of the present invention has good air permeability and moisture permeability, and has a smooth appearance and antifouling property.
• a preferred silver-finished artificial leather having a narrow opening hole formed on the surface has excellent wear resistance and durability in addition to these characteristics.
• the artificial leather with silver tone of the present invention is useful as shoes, especially uppers for sports sports, gloves, seats and / or backrests of chairs, coats and other clothes.

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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)
• Laminated Bodies (AREA)

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• 1994
  • 1994-03-10 CN CN94190073A patent/CN1051345C/zh not_active Expired - Lifetime
  • 1994-03-10 WO PCT/JP1994/000388 patent/WO1994020665A1/ja not_active Ceased
  • 1994-03-10 DE DE69418266T patent/DE69418266T2/de not_active Expired - Lifetime
  • 1994-03-10 US US08/284,661 patent/US5518800A/en not_active Expired - Lifetime
  • 1994-03-10 EP EP94909298A patent/EP0640715B1/en not_active Expired - Lifetime
  • 1994-03-10 KR KR1019940703082A patent/KR100188849B1/ko not_active Expired - Lifetime
  • 1994-03-22 TW TW83102486A patent/TW294738B/zh not_active IP Right Cessation

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