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
  • D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
  • D06N3/0065—Organic pigments, e.g. dyes, brighteners
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0006—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using woven fabrics
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
  • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
  • D06N3/0025—Rubber threads; Elastomeric fibres; Stretchable, bulked or crimped fibres; Retractable, crimpable fibres; Shrinking or stretching of fibres during manufacture; Obliquely threaded fabrics
  • D06N3/0027—Rubber or elastomeric fibres
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
  • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
  • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/10—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 by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
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  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/04—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 by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/10—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 by reactions only involving carbon-to-carbon unsaturated bonds with styrene-butadiene copolymerisation products or other synthetic rubbers or elastomers except polyurethanes
  • D06N3/106—Elastomers
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  • 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
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  • D06N2201/00—Chemical constitution of the fibres, threads or yarns
  • D06N2201/02—Synthetic macromolecular fibres
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  • D06N2209/00—Properties of the materials
  • D06N2209/08—Properties of the materials having optical properties
  • D06N2209/0807—Coloured
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  • D06N2209/00—Properties of the materials
  • D06N2209/08—Properties of the materials having optical properties
  • D06N2209/0807—Coloured
  • D06N2209/0815—Coloured on the layer surface, e.g. ink
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  • D06N2209/00—Properties of the materials
  • D06N2209/08—Properties of the materials having optical properties
  • D06N2209/0807—Coloured
  • D06N2209/0823—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
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  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/26—Vehicles, transportation
  • D06N2211/263—Cars
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  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/28—Artificial leather

Definitions

• the present invention relates to artificial leather and a light transmitting device using the same.
• Suede-like artificial leather made of ultrafine fibers and polymer elastic material has excellent properties that natural leather does not have in terms of durability and uniformity. Taking advantage of these characteristics, suede-like artificial leather has been used in a wide range of applications such as clothing, furniture and interior materials for automobiles. In recent years, there has been a need for further diversification, and studies are being conducted on home appliances, automobile consoles, etc. as various skin materials.
• the brightness index in the CIE1976L * a * b * color space (hereinafter, may be simply referred to as L * value) is 50 or less.
• Dark-colored artificial leather has poor light transmission, and may not transmit light depending on conditions such as the color of the artificial leather and the amount of light of the light source. Therefore, in the technique disclosed in Patent Documents 1 and 2, a cutout portion is provided or a light transmitting portion formed by forming a non-woven fabric into a film is provided so that a portion that substantially blocks light is not provided. ing.
• the artificial leather in the portion where light is desired to be transmitted is removed or fused, there is a problem that the texture, texture and dignity of the artificial leather are impaired.
• the present invention has been made in view of the above circumstances, and an object thereof is artificial leather having a medium concentration or higher of dark color, yet having light transmission while maintaining its texture and tactile sensation.
• the purpose is to provide leather, and a light transmissive device using the leather.
• the present inventors have set the color difference between the design surface and the opposite surface in a specific range in artificial leather having a specific thickness and texture, thereby forming a cutout portion or the like.
• the artificial leather of the present invention is an artificial leather containing a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 8 ⁇ m or less and a polymer elastic body as constituent elements, and the thickness of the artificial leather is described above. Is 0.4 mm or more and 1.2 mm or less, the texture of the artificial leather is 80 g / m 2 or more and 450 g / m 2 or less, and one surface of the artificial leather is made of a dye and / or a pigment. It is a colored design surface and satisfies the following formulas (1) to (3).
• L * 1 is the CIE1976L * a * b * color space of the design surface
• L * 0 is the CIE1976L * a * b * color space of the surface opposite to the design surface
• the brightness index (L * value) and ⁇ L * in are the difference between the L * value of the design surface and the L * value of the surface opposite to the design surface (CIELAB1976ab brightness difference, L * 1 -L * 0 ). be.
• the brightness index is a value measured under the conditions of the CIE standard light source D65 and the viewing angle of 10 °.
• the fiber entanglement is dyed with a dye.
• the light transmitting device of the present invention includes at least one light source and the artificial leather as components, and the artificial leather is placed on the light source.
• the present invention it is possible to obtain an artificial leather having excellent light transmission while maintaining the texture and feel of the artificial leather.
• the artificial leather of the present invention can be suitably used for home appliances, automobile consoles, etc. because it has excellent light transmission even though it is a medium- or dark-colored artificial leather that has conventionally had poor light transmission.
• artificial leather having fluff when used, it can be made into a high-class artificial leather having light transmission while maintaining the fluffy feeling and texture of suede leather, and can be effectively used for the above-mentioned applications. ..
• the artificial leather of the present invention is an artificial leather containing a fiber entangled body made of ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 8 ⁇ m or less and a polymer elastic body as constituent elements, and the thickness of the artificial leather is described above. Is 0.4 mm or more and 1.2 mm or less, the texture of the artificial leather is 80 g / m 2 or more and 450 g / m 2 or less, and one surface of the artificial leather is made of a dye and / or a pigment. It is a colored design surface and satisfies the following formulas (1) to (3).
• L * 1 is the CIE1976L * a * b * color space of the design surface
• L * 0 is the CIE1976L * a * b * color space of the surface opposite to the design surface
• the brightness index (L * value) and ⁇ L * in are the difference between the L * value of the design surface and the L * value of the surface opposite to the design surface (CIELAB1976ab brightness difference, L * 1 -L * 0 ). be.
• the brightness index is a value measured under the conditions of the CIE standard light source D65 and the viewing angle of 10 °. The components thereof will be described in detail below, but the present invention is not limited to the scope described below as long as the gist thereof is not exceeded.
• the ultrafine fibers constituting the fiber entanglement which is one of the constituent elements of the artificial leather of the present invention, have an average single fiber diameter of 0.1 ⁇ m or more and 8 ⁇ m or less.
• the average single fiber diameter By setting the average single fiber diameter to 0.1 ⁇ m or more, preferably 0.2 ⁇ m or more, more preferably 0.3 ⁇ m or more, artificial leather having good dyeing fastness is obtained, and artificial leather having particularly good light fastness is particularly good. It becomes.
• it is 8.0 ⁇ m or less, preferably 4.0 ⁇ m or less, and more preferably 2.0 ⁇ m or less, the leather has a good texture.
• the average single fiber diameter of the ultrafine fibers shall be calculated by the following method.
• the average single fiber diameter of the ultrafine fibers shall be a value measured and calculated as follows. (1) The fiber entangled body is cut to expose the cross section in the thickness direction to be the observation surface. (2) Take a scanning electron microscope (SEM) photograph of the cross section in the thickness direction. (3) 100 circular or nearly circular elliptical ultrafine fibers are randomly selected. (4) The single fiber diameter of the selected ultrafine fiber is measured, and the average value thereof is calculated.
• the ultrafine fibers of the present invention include polyesters such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, polyamides such as 6-nylon and 66-nylon, acrylic, polyethylene and polypropylene.
• polyester fibers made of polymers such as polyethylene terephthalate, polybutylene terephthalate and polytrimethylene terephthalate are preferably used because they are excellent in strength, dimensional stability, light resistance and dyeability. Further, in the fiber entanglement, ultrafine fibers made of different materials can be mixed as long as the object of the present invention is not impaired.
• Inorganic particles such as titanium oxide particles, lubricants, pigments, heat stabilizers, ultraviolet absorbers, conductive agents, heat storage agents, antibacterial agents, etc. are added to the ultrafine fibers constituting the fiber entanglement, depending on various purposes. can do.
• the cross-sectional shape of the ultrafine fibers constituting the fiber entanglement can be a polygonal shape such as an ellipse, a flat surface, or a triangular shape, or a deformed cross-sectional shape such as a fan shape or a cross shape.
• the fiber entanglement which is one of the constituent elements of the artificial leather of the present invention, comprises the above-mentioned ultrafine fibers.
• Examples of the form of the fiber entanglement include woven fabrics, knitted fabrics, non-woven fabrics, and fiber entanglements in which a polymer elastic body is filled in these fiber structures, and the costs and characteristics required for each application and purpose are included. It can be used properly according to the situation. Woven fabrics and knitted fabrics are preferably used in terms of cost, and non-woven fabrics and fiber entangled bodies filled with polymer elastic bodies are preferably used in terms of quality due to a rich texture and fine fluff.
• a woven or knitted fabric When a woven or knitted fabric is used as a fiber entanglement, examples of the woven fabric include plain weave, twill weave, satin weave, and various woven fabrics based on their woven structure. Further, as the knitting, any of warp knitting, weft knitting represented by tricot knitting, lace knitting and various knittings based on these knitting structures can be adopted.
• non-woven fabric When a non-woven fabric is used as a fiber entanglement, it is expressed in various categories such as general short-fiber non-woven fabric, long-fiber non-woven fabric, needle punch non-woven fabric, paper-made non-woven fabric, spunbond non-woven fabric, melt-blow non-woven fabric, and electro-spinning non-woven fabric. All non-woven fabrics can be applied.
• the non-woven fabric is preferable in terms of the texture with a sense of fulfillment and the quality due to the fine fluff.
• the fiber entanglement in which the polymer elastic body is filled in these fiber entanglements is more preferably used because it is excellent in the durability of the artificial leather and the abrasion resistance of the surface of the artificial leather.
• the artificial leather of the present invention from the viewpoint of excellent mechanical strength, it is a preferable embodiment to include a woven or knitted material inside the structure.
• the fiber entanglement includes a woven or knitted fabric
• synthetic fibers made of polyester, polyamide, polyethylene, polypropylene, or copolymers thereof are preferably used as the threads constituting the woven or knitted fabric.
• synthetic fibers made of polyester, polyamide and their copolymers can be used alone or in combination or in combination.
• the yarn constituting the woven or knitted fabric a filament yarn, a spun yarn, a blended yarn of a filament and a short fiber, or the like can be used as the yarn constituting the woven or knitted fabric.
• the woven or knitted fabric contained in the fiber entanglement comprises a composite fiber in which two or more kinds of polymers are combined in a side-by-side type or an eccentric core sheath type (hereinafter, may be referred to as a side-by-side type or the like composite fiber).
• Woven and knitted fabrics can also be used.
• a side-by-side type or the like composite fiber composed of two or more kinds of polymers having an intrinsic viscosity (IV) difference, different internal strains occur between the two components due to stress concentration on the high viscosity side during stretching.
• Examples of the woven fabric included in the fiber entanglement include plain weave, twill weave, satin weave, and various woven fabrics based on their weaving structure as described above. Further, as the knitting, any of warp knitting, weft knitting represented by tricot knitting, lace knitting and various knittings based on these knitting structures can be adopted. Among them, woven fabrics are preferable from the viewpoint of processability, and plain weave fabrics are particularly preferably used from the viewpoint of cost. Further, the weaving density of the woven fabric can be appropriately set depending on the total fineness of the threads and the equipment and conditions for entwining the nonwoven fabric and the woven or knitted fabric, which will be described later.
• the fiber entanglement is dyed with a dye.
• the color difference referred to here refers to the difference between the a * value and the b * value in the CIE1976L * a * b * color space, and both the ⁇ a * value and the ⁇ b * value are preferably within ⁇ 20 and more preferably within ⁇ 10.
• the color difference is a value measured under the condition of the CIE standard light source D65 and the condition of the viewing angle of 10 °. If the same type of hue as the design surface is used, a more unified hue can be obtained.
• the ⁇ a * value and the ⁇ b * value referred to here are values obtained by a method described later.
• polymer elastic body In the artificial leather of the present invention, the morphological stability of the artificial leather and the abrasion resistance of the surface are improved by including the polymer elastic body inside the fiber entangled body as described above.
• polyurethane polyurethane
• SBR styrene butadiene rubber
• NBR nitrile rubber
• acrylic resin and the like can be used as the polymer elastic body, among others.
• polyurethane it is a preferable embodiment to use polyurethane as a main component. By using polyurethane, it is possible to obtain artificial leather having a full feel, a leather-like appearance, and physical characteristics that can withstand actual use.
• both the organic solvent-based polyurethane used in the state of being dissolved in the organic solvent and the water-dispersed polyurethane used in the state of being dispersed in water are both.
• a polyurethane obtained by reacting a polymer diol with an organic diisocyanate and a chain extender is preferably used.
• the polymer elastic body inside the fiber entanglement contains various additives such as pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based, and oxidation of phenol-based, sulfur-based and phosphorus-based materials.
• additives such as pigments such as carbon black, flame retardants such as phosphorus-based, halogen-based and inorganic-based, and oxidation of phenol-based, sulfur-based and phosphorus-based materials.
• Inhibitors benzotriazole-based, benzophenone-based, salicylate-based, cyanoacrylate-based and oxalic acid anilide-based UV absorbers, hindered amine-based and benzoate-based light stabilizers, hydrolysis-resistant stabilizers such as polycarbodiimide, etc. It can contain plasticizers, antistatic agents, surfactants, coagulation modifiers, dyes and the like.
• the content of the polymer elastic body inside the fiber entangled body can be appropriately adjusted in consideration of the type of the polymer elastic body to be used, the manufacturing method of the polymer elastic body, and the texture and physical properties.
• the content of the polymer elastic body is preferably 5% by mass or more and 80% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and further preferably 15% by mass with respect to the mass of the fiber entangled body. It is 45% by mass or less.
• the artificial leather of the present invention contains the above-mentioned fiber entangled body and a polymer elastic body as constituent elements.
• the thickness of the artificial leather of the present invention is 0.4 mm or more and 1.2 mm or less.
• the thickness of the artificial leather is 0.4 mm or more, preferably 0.5 mm or more, more preferably 0.6 mm or more, the strength and elongation required for the artificial leather can be obtained.
• it is 1.2 mm or less, preferably 1.0 mm or less, and more preferably 0.8 mm or less, the artificial leather which is the object of the present invention can easily obtain the light transmission.
• the thickness of artificial leather refers to the value measured and calculated by the following procedure in accordance with "8.4 Thickness A method" of JIS L1096: 2010 "Fabric test method for woven fabrics and knitted fabrics”. ..
• the measurement sample is pre-dried in an environment with a relative humidity of 10 to 25% and a temperature of less than 50 ° C., and then left in a room in a standard state to adjust the amount in a constant amount.
• the basis weight of the artificial leather of the present invention is 80 g / m 2 or more and 450 g / m 2 or less.
• the basis weight of the artificial leather is 80 g / m 2 or more, preferably 100 g / m 2 or more, more preferably 120 g / m 2 or more, the artificial leather has durability.
• the content is set to 450 g / m 2 or less, preferably 400 g / m 2 or less, more preferably 350 g / m 2 or less, the artificial leather, which is the object of the present invention, is more easily obtained.
• the basis weight of artificial leather is measured by the following procedure in accordance with "8.3.2. And points to the calculated value.
• (1) The measurement sample is pre-dried in an environment with a relative humidity of 10 to 25% and a temperature of less than 50 ° C., and then left in a room in a standard state. Take a sheet, weigh the mass (g) in each standard state, calculate the mass per 1 m 2 (g / m 2 ) by the following formula, calculate the average value, and round to one digit after the decimal point.
• Sm W / A here, Sm: Mass per unit area in standard state (g / m 2 ) W: Mass of test piece in standard state (g) A: Area of test piece (m 2 ) Is.
• the artificial leather of the present invention has a design surface whose one surface is colored with a dye and / or a pigment and satisfies the following formulas (1) to (3).
• L * 1 ⁇ 55 ... ⁇ (1)
• L * 1 is the CIE1976L * a * b * color space of the design surface
• L * 0 is the CIE1976L * a * b * color space of the surface opposite to the design surface
• the brightness index (L * value) and ⁇ L * in are the difference between the L * value of the design surface and the L * value of the surface opposite to the design surface (CIELAB1976ab brightness difference, L * 1 -L * 0 ). be.
• the brightness index is a value measured under the conditions of the CIE standard light source D65 and the viewing angle of 10 °.
• L * 1 ⁇ 55 as shown in the above equation (1) means that the design surface has a medium dark color to a dark color. According to the present invention, it is possible to obtain artificial leather having excellent light transmission even in a dark color such as L * 1 ⁇ 30.
• L * 0 > 50 means that the color is lighter than the design surface when measured from the surface opposite to the design surface, and the above equation (3).
• ⁇ L * ⁇ -5 that is, the color difference due to ⁇ L * is more than a certain level, so that the light transmission can be improved even on a dark-colored design surface.
• L * 0 > 60 and more preferably L * 0 > 70.
• the upper limit is preferably L * 0 ⁇ 90 from the viewpoint of designability, that is, so as to be less susceptible to the influence of the hue on the opposite side of the design surface.
• ⁇ L * ⁇ -5 is preferably ⁇ L * ⁇ -10, and more preferably ⁇ L * ⁇ -15.
• the artificial leather of the present invention can be obtained, for example, by using an ultrafine fiber-expressing fiber composed of two or more kinds of polymer substances having different solubility in a solvent.
• the ultrafine fiber-expressing fiber is a sea-island type fiber in which two components of thermoplastic resin having different solubility in a solvent are used as a sea component and an island component, and the sea component is dissolved and removed using a solvent to make the island component into an ultrafine fiber. It is possible to adopt a peelable composite fiber in which composite fibers or two-component thermoplastic resins are alternately arranged in a radial or multilayer manner on the fiber surface and split into ultrafine fibers by peeling and splitting by solvent treatment. ..
• the sea-island type composite fiber can provide an appropriate void between the island components, that is, between the ultrafine fibers inside the fiber bundle by removing the sea component, so that it is also possible from the viewpoint of the flexibility and texture of the base material. It is preferably used.
• sea-island type composite fiber For the production of sea-island type composite fiber, a polymer mutual arrangement method in which two components of sea component and island component are mutually arranged and spun using a sea-island type composite base, and two components of sea component and island component are mixed.
• a mixed spinning method or the like can be used, but a method for producing a sea-island type composite fiber by a polymer array method is more preferably used in that ultrafine fibers having a uniform fineness can be obtained.
• the ultrafine fibers are in the form of a non-woven fabric (ultrafine fiber web) in the fiber entanglement.
• a non-woven fabric By using a non-woven fabric, a uniform and elegant appearance and texture can be obtained.
• the non-woven fabric (ultrafine fiber web) may be in either a short fiber non-woven fabric or a long fiber non-woven fabric.
• the fiber length of the ultrafine fibers in the case of a short fiber non-woven fabric can be appropriately selected depending on the form of the non-woven fabric.
• the fiber length in the case of a normal short fiber non-woven fabric is preferably 25 mm or more and 90 mm or less.
• the fiber length is preferably 0.1 mm or more and 10 mm or less.
• the fiber length By setting the fiber length to 10 mm or less, a stable suspension can be obtained, and unevenness in the basis weight and thickness of the nonwoven fabric can be suppressed. Further, by setting the fiber length to 0.1 mm or more, it is possible to suppress fluffing from the non-woven fabric. Further, since the ultrafine fiber generation type fiber of the present invention promotes entanglement between fibers, it is preferable to perform a crimping process. A known method can be used for the crimping process and the cutting process.
• the obtained raw cotton is used as a fiber web with a cloth wrapper or the like and entangled to obtain a non-woven fabric.
• a needle punch, a water jet punch, or the like can be used as a method of entwining the fiber webs to obtain a nonwoven fabric.
• the basis weight of the fiber web can be appropriately set in consideration of the design of the final product, the dimensional change in the subsequent process, the characteristics of the processing machine, and the like.
• entangle and integrate the woven and knitted fabric and the fiber entangled body made of the ultrafine fiber generating type fiber to obtain a laminated sheet of the nonwoven fabric made of the ultrafine fiber generating type fiber and the woven and knitted fabric.
• a method of entwining and integrating the two a method such as a needle punch or a water jet punch can be used.
• the entanglement treatment by needle punching is a preferable embodiment from the viewpoint of adhesiveness and product quality.
• the fiber entangled body made of the ultrafine fiber-generating fibers and the laminated sheet of the woven or knitted fabric thus obtained are dry heat, wet heat, or both at the stage before the polymer elastic body is applied. It is a preferable embodiment to shrink the fiber and further increase the density.
• This shrinkage treatment can be performed before or after the expression of the ultrafine fibers, but before the generation of the ultrafine fibers, the characteristics of the sea component polymer of the ultrafine fiber generation type fibers can be utilized for the shrinkage. It is a preferable embodiment to carry out the shrinkage treatment. Further, the range of the area shrinkage rate of the laminated sheet in this shrinkage step is preferably 15% or more and 35% or less.
• the area shrinkage rate By setting the area shrinkage rate to 15% or more, the effect of improving the quality due to shrinkage can be preferably obtained. Further, by setting the area shrinkage rate to 35% or less, it is possible to leave room for shrinkage in the woven or knitted fabric integrated with the non-woven fabric, so that it is possible to efficiently shrink the woven or knitted fabric after applying the polymer elastic body. Become.
• the range of the more preferable area shrinkage rate is 1% or more and 30% or less, and more preferably 15% or more and 25% or less.
• the area shrinkage rate is measured by calculating the length before and after machining in the shrinkage process, the shrinkage rate in the length direction from the width, and the shrinkage rate in the width direction, and the length shrinkage rate calculated by the following formula.
• Width shrinkage rate Width after shrinkage processing / Width before shrinkage processing
• Area shrinkage rate (%) (1- (1-Length shrinkage rate) x (1) -Width shrinkage rate)) x 100.
• the shrinkage method known methods such as hot water shrinkage, steam shrinkage, and dry heat shrinkage can be adopted.
• the time and temperature of the shrinkage treatment may be adjusted to the above-mentioned area shrinkage rate depending on the shrinkage method to be adopted, the type of fibers constituting the fiber entanglement, and the like.
• a laminated sheet of a fiber entangled body made of the above-mentioned ultrafine fiber-generating fibers and a woven or knitted fabric is treated to develop ultrafine fibers having an average single fiber diameter of 0.1 ⁇ m or more and 8 ⁇ m or less.
• the method for treating the generation of ultrafine fibers include a method in which one of the resins constituting the ultrafine fiber generation type fiber is dissolved with a solvent.
• a method of dissolving the sea component is preferable for the ultrafine fiber-generating type sea-island composite fiber in which the sea component is made of an easily soluble polymer and the island component is made of a poorly soluble polymer.
• the solvent for dissolving the sea component when the sea component is a polyolefin such as polyethylene or polystyrene, an organic solvent such as toluene or trichlorethylene is used.
• an alkaline aqueous solution such as sodium hydroxide can be used.
• this ultrafine fiber generation processing (desealing treatment) can be performed by immersing a fiber entangled body made of ultrafine fiber generation type fibers in a solvent and constricting the liquid.
• a process of imparting a polymer elastic body to the obtained fiber entangled body containing the ultrafine fibers is performed.
• a method of expressing the ultrafine fibers from the ultrafine fiber-expressing type fibers and the treatment of imparting a polymer elastic body can be adopted first.
• the polymer elastic body grips the ultrafine fibers, so that the ultrafine fibers do not fall off and can withstand longer-term use.
• the polymer elastic body has a structure in which the ultrafine fibers are not gripped, so that an artificial leather having a good texture can be obtained. Which one should be performed first can be appropriately selected depending on the type of polyurethane used and the like.
• the polymer elastic body when the polymer elastic body is applied after the expression treatment of the ultrafine fibers, it is preferable to provide a step of applying the water-soluble resin between both steps.
• the step of applying the water-soluble resin By providing the step of applying the water-soluble resin, the surface of the fiber bundle of the ultrafine fibers and the fibers constituting the woven or knitted fabric is protected by the water-soluble resin, and the surface of the fiber bundle of the ultrafine fibers or the fibers constituting the woven or knitted fabric is formed.
• the portion directly bonded to the polymer elastic body is not continuous but intermittently exists, and the bonding area can be appropriately suppressed.
• polyvinyl alcohol polyethylene glycol, saccharides, starch and the like can be used.
• polyvinyl alcohol having a saponification degree of 80% or more is preferably used.
• Examples of the method of applying the water-soluble resin to the fiber entanglement include a method of impregnating the fiber entanglement with an aqueous solution of the water-soluble resin and drying it.
• the drying conditions such as the drying temperature and the drying time are preferably such that the temperature of the fiber entangled body itself to which the water-soluble resin is applied is suppressed to 110 ° C. or lower from the viewpoint of suppressing the shrinkage of the woven or knitted fabric.
• the amount of the water-soluble resin applied is preferably 1 to 30% by mass with respect to the mass of the fiber entangled immediately before the application.
• the applied amount is preferably 1 to 30% by mass with respect to the mass of the fiber entangled immediately before the application.
• a step of half-cutting a fiber entangled body (precursor sheet of artificial leather) to which a polymer elastic body is applied can be performed in the plane direction.
• the productivity of artificial leather can be improved.
• a method of sandwiching a non-woven fabric layer made of ultrafine fiber generation type fibers between woven and knitted fabric layers is adopted as a method of laminating woven and knitted fabrics, the precursor sheet is cut in half and the inner surface is made into a fluffy surface.
• this is a preferred embodiment as a method for achieving fine quality.
• the artificial leather of the present invention preferably has fluff on at least one side.
• the fluff treatment can be performed by buffing the surface of the precursor sheet of artificial leather with sandpaper, roll sander, or the like. In particular, by using sandpaper, uniform and dense naps can be formed. Further, in order to form uniform fluff on the surface of the precursor sheet of artificial leather, it is preferable to reduce the grinding load.
• the obtained artificial leather precursor sheet can be dyed.
• Dyeing is performed so that the brightness index (L * value) in the CIE1976L * a * b * color space of the surface opposite to the design surface is within the range of the present invention.
• a dyeing method there is no particular problem even if a precursor sheet of the artificial leather is prepared in advance and dyed with a general dye suitable for the fiber material.
• a dye that matches the fiber base material of artificial leather can be used. If the fiber base material is a polyester fiber, a disperse dye is used, and if the fiber base material is a polyamide fiber, an acid dye, a gold-containing dye, etc. are usually used. The dye used for dyeing can be used.
• Dyeing is preferably performed by using a disperse dye, a cationic dye or another reactive dye, and using a high temperature and high pressure dyeing machine to soften the texture of the artificial leather base material to be dyed.
• the artificial leather of the present invention has a design surface colored with a dye and / or a pigment.
• the coloring of the design surface is within the range defined by the present invention by ⁇ L * , which is the difference between the L * value of the design surface and the L * value of the design surface and the L * value of the surface opposite to the design surface. Colored to meet.
• printing techniques such as dye printing and pigment printing can be used.
• dyes that match the fiber base material of artificial leather can be used. If the fiber base material is a polyester fiber, a disperse dye, if the fiber base material is a polyamide fiber, an acidic dye, a gold-containing dye, etc., are usually polyamide. The dye used when dyeing can be used.
• the printing method is not limited to any method such as transfer printing, screen printing, and inkjet printing.
• the pigment print a pigment mixed with a binder resin can be used, and as the binder resin, a urethane resin, an acrylic resin, a silicone resin, or the like can be used, and there is no particular limitation.
• the printing method is not limited to any method such as transfer printing, screen printing, and inkjet printing.
• a finishing treatment such as a softener such as silicone, an antistatic agent, a water repellent agent, a flame retardant and a light resistant agent can be applied, and the finishing treatment can be performed after dyeing or in the same bath as dyeing.
• a flame retardant treatment known halogen-based flame retardants such as bromine and chlorine and non-halogen flame retardants such as phosphorus can be used. It can also be applied by coating.
• finishing treatments are not limited before or after the formation of the colored layer, but in order to form a uniform colored layer, the finishing treatment is preferably after the formation of the colored layer. Further, these finishing agents can be processed at the same time as forming the colored layer, but as described above, in order to form a uniform colored layer, the finishing treatment is preferably after forming the colored layer.
• the artificial leather of the present invention is light-transmitting, it is suitably used for a light-transmitting device.
• the light transmitting device includes at least one light source and the artificial leather as a component, and the artificial leather is placed on the light source. Since the artificial leather of the present invention is light-transmitting, the light of the light source can be visually recognized through the artificial leather of the present invention.
• the light source constituting the light transmission device of the present invention is not particularly limited, but since it is necessary to incorporate it in the device, a small light source such as a light emitting diode (LED) or electroluminescence (EL) that emits electric light is preferable. Used.
• the wavelength that can be used is not particularly limited, and there is no problem as long as it is visible light of 380 nm to 780 nm.
• the illuminance of the light source is not particularly limited, but 2000 lp or more is preferable from the viewpoint of light transmission.
• the artificial leather When used in the above-mentioned light-transmitting device, the artificial leather is made to satisfy the above formulas (1) to (3) at least in the portion requiring light transmission, but the color tone of the other parts not requiring light transmission is the same. It is possible to compose with the same design aspect or to compose with a free design.
• the artificial leather of the present invention will be described in more detail using examples, but the present invention is not limited to these examples.
• the evaluation method used in the examples and the measurement conditions thereof will be described. However, in the measurement of each physical property, if there is no particular description, the measurement is performed based on the above method.
• L * 1 CIE1976L * a * b * of the design surface
• Brightness index (L * value) in the color space L * 0 : CIE1976L * a * b * Brightness index (L * value) in the color space on the surface opposite to the design surface
• ⁇ L * is the difference between the L * value of the design surface and the L * value of the surface opposite to the design surface (CIELAB1976ab brightness difference, L * 1 -L * 0 ) a * 1 : CIE1976L * a of the design surface.
• ⁇ a * is the difference between the a * value of the design surface and the a * value of the surface opposite to the design surface (CIELAB1976a * difference, a * 1 -a * 0 ).
• ⁇ b * is the difference between the b * value of the design surface and the b * value of the surface opposite to the design surface (CIELAB1976b * difference, b * 1 -b * 0 ). Is.
• the measurement was carried out by incident from the opposite side of the design surface (the back side of the design surface). Assuming that 0.2% or more has light transmission, it is described as ⁇ (B) in Table 1, and those having better light transmission of 3.0% or more are described as ⁇ (A) in Table 1. .. If it is less than 0.2%, it is described as ⁇ (C) as having no light transmission.
• the one that is preferably used for the light transmission device is ⁇ (A)
• the one that can be used is ⁇ (B)
• a comprehensive judgment was made by setting x (C) as a device that cannot be used as a light transmission device.
• Example 1 ⁇ Raw cotton> Polyethylene terephthalate is used as the island component, polystyrene is used as the sea component, and a sea-island type composite base with 16 islands is used for melt-spinning at an island / sea mass ratio of 80/20, then stretched and crimped. Then, it was cut to a length of 51 mm to obtain raw cotton of a sea-island type composite fiber.
• needle punching was performed at a punching number (density) of 2500 / cm 2 , and a laminate consisting of a non-woven fabric made of ultrafine fiber-generating fibers having a basis weight of 740 g / m 2 and a thickness of 3.4 mm and a heat-shrinkable woven fabric was applied. I got a sheet.
• the laminated sheet obtained in the above step is treated with hot water at a temperature of 96 ° C. and shrunk, then impregnated with an aqueous solution of polyvinyl alcohol (hereinafter, may be abbreviated as PVA) and hot air at a temperature of 110 ° C. By drying for 10 minutes at the same time, a sheet substrate having a PVA mass of 7.6% by mass with respect to the mass of the laminated sheet was obtained.
• PVA polyvinyl alcohol
• the sheet substrate thus obtained is immersed in trichlorethylene to dissolve and remove polystyrene, which is a sea component, and a desealed sheet formed by entwining ultrafine fibers having an average single fiber fineness of 4.4 ⁇ m and a plain woven fabric.
• a desea sheet made of a non-woven fabric made of ultrafine fibers and a plain cloth thus obtained is immersed in a polyurethane dimethylformamide (hereinafter, may be abbreviated as DMF) solution having a solid content concentration adjusted to 12%.
• DMF polyurethane dimethylformamide
• the polyurethane was coagulated in an aqueous solution having a DMF concentration of 30%.
• PVA and DMF are removed with hot water and dried with hot air at a temperature of 110 ° C. for 10 minutes.
• a coalesced precursor sheet was obtained.
• the precursor sheet of the fiber entanglement thus obtained is cut in half in the thickness direction, the nonwoven fabric layer inside the precursor sheet is cut in half perpendicular to the thickness direction, and the half-cut sheet surface is sandpaper count 320. Grinding with endless sandpaper was performed to form a fluffy surface on the surface layer, and a fiber entangled body having a thickness of 0.90 mm was obtained.
• the fiber entanglement thus obtained is dyed in a light gray color having an L * value of 50 or more with a disperse dye using a liquid flow dyeing machine, then reduced and washed, and dried in a dryer. After that, the pigment was printed on the design surface in the screen printing machine. In the pigment print, black pigment and urethane resin were used as binders. In this way, a fiber entangled body having an L * value of 20.08 on the design surface and an L * value of 70.86 on the back side of the design surface was obtained.
• Example 2 ⁇ Raw cotton-fiber entanglement> The same as in Example 1 was used.
• Example 3 ⁇ Raw cotton-fiber entanglement> The same as in Example 1 was used.
• Example 4 ⁇ Raw cotton-fiber entanglement> The same as in Example 1 was used.
• Example 5 ⁇ Raw cotton-fiber entanglement> The same as in Example 1 was used.
• the ⁇ a * value was within ⁇ 20, but the ⁇ b * value was 39.97, which was ⁇ 20 or more, so that the white color on the opposite side of the design surface was slightly visible from the design surface, and the color was flickered. It was confirmed that the texture was good and it could be used for a light transmitting device.
• Table 1 The results are shown in Table 1.
• Example 6 ⁇ Raw cotton-fiber entanglement> The same as in Example 1 was used.
• the fiber entanglement thus obtained is dyed in a gray color with a disperse dye using a liquid flow dye to have an L * value of 50 or less, then reduced and washed, and dried in a dryer. After that, a black pigment was printed on the design surface in a screen printing machine. In this way, a fiber entangled body having an L * value of 22.50 on the design surface and an L * value of 44.02 on the back side of the design surface was obtained.
• the artificial leathers of Examples 1 to 6 had a spectral transmittance of 0.2% or more and had a light transmittance.
• the artificial leathers of Comparative Examples 1 to 3 had a spectral transmittance of 0.0% and no light transmittance.
• Example 1 had a dark black design surface equal to or higher than that of Comparative Example 1 but had good light transmission.

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