WO2022107720A1 - 皮革様シート、及びそれを背表材として用いた背負い鞄 - Google Patents

皮革様シート、及びそれを背表材として用いた背負い鞄 Download PDF

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Publication number
WO2022107720A1
WO2022107720A1 PCT/JP2021/041913 JP2021041913W WO2022107720A1 WO 2022107720 A1 WO2022107720 A1 WO 2022107720A1 JP 2021041913 W JP2021041913 W JP 2021041913W WO 2022107720 A1 WO2022107720 A1 WO 2022107720A1
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WIPO (PCT)
Prior art keywords
leather
layer
black pigment
sheet
reflectance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/041913
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English (en)
French (fr)
Japanese (ja)
Inventor
哲哉 芦田
寛斉 原
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray Co Ltd
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Kuraray Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kuraray Co Ltd filed Critical Kuraray Co Ltd
Priority to US18/253,122 priority Critical patent/US20230416982A1/en
Priority to JP2022563741A priority patent/JP7847542B2/ja
Priority to CN202180076428.2A priority patent/CN116438058B/zh
Priority to EP21894594.7A priority patent/EP4249671A4/en
Publication of WO2022107720A1 publication Critical patent/WO2022107720A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—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
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45F—TRAVELLING OR CAMP EQUIPMENT: SACKS OR PACKS CARRIED ON THE BODY
    • A45F3/00—Travelling or camp articles; Sacks or packs carried on the body
    • A45F3/04—Sacks or packs carried on the body by means of two straps passing over the two shoulders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
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    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/026—Knitted fabric
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • 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
    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
    • 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
    • D06N3/0086—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
    • D06N3/0095—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 inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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    • B32B2439/06—Bags, sacks, sachets
    • 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
    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0218—Vinyl resin fibres
    • D06N2201/0227—Aromatic vinyl resin, e.g. styrenic (co)polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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    • D06N2213/00—Others characteristics
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Definitions

  • the present invention relates to a leather-like sheet having excellent detectability by LIDAR (Laser Imaging Detection and Ringing), and a backpack using the same as a back surface material.
  • LIDAR Laser Imaging Detection and Ringing
  • LIDAR Light Detection and Ranging
  • LIDAR sensors As safety devices used in LIDAR is accelerating.
  • the purpose of adopting LIDAR sensors for autonomous driving technology of automobiles is to suppress traffic accidents by detecting vehicles, people, objects, etc. around the driven automobile in advance and reflecting them in the driving situation. be.
  • the LIDAR sensor which is being adopted in the automatic driving technology of automobiles, often uses pulsed laser light which is near infrared rays of 905 to 1600 nm. Since such pulsed laser light has high reflectivity, the distance measurement accuracy is excellent.
  • leather-like sheets such as artificial leather having a silver-like resin layer are used as a material for bags, clothing, shoes, etc.
  • the resin layer of the leather-like sheet is usually colored and used.
  • the leather-like sheet having a silver-like resin layer colored in black is the most widely used.
  • Patent Document 1 includes a base material layer, a resin layer provided on the base material layer, and a surface layer provided on the resin layer, and the resin layer contains hygroscopic fine particles and infrared rays.
  • a synthetic leather containing a reflective pigment and having a surface layer of 0.2 g / m 2 or more and 1 g / m 2 or less of hygroscopic fine particles. Since such synthetic leather contains an infrared reflective pigment in the resin layer, it does not easily become hot in sunlight even if it is black or dark, and the outermost layer is on the resin layer. Therefore, it is disclosed that it is also excellent in fading resistance.
  • the infrared reflective pigment discloses that the average reflectance in the 780 to 1800 nm (near infrared region) is 20% or more, and the average reflectance in the 400 to 760 nm (visible light region) is 70% or more. ..
  • Patent Document 2 describes at least the production of a black near-infrared reflective pigment in which a calcium compound, a titanium compound and a manganese compound are mixed by a wet pulverization method and fired at a temperature higher than 1100 ° C.
  • a method for producing a black near-infrared reflective pigment wherein the black near-infrared reflective pigment has a perovskite phase as a main phase and a BET specific surface area is 1.0 m 2 / g or more and less than 3.0 m 2 / g. do.
  • a resin layer mainly composed of polyurethane having a thickness of 30 to 100 ⁇ m containing 2% or more of perylene black with respect to the resin weight is used as an upper layer, and a polyurethane containing carbon black is mainly used as a lower layer.
  • an artificial leather with a black grain surface layer which is characterized in that a resin layer is laminated.
  • the LIDAR sensor which is being adopted in automated driving technology, has a problem that the detection sensitivity of black objects is low.
  • the pulsed laser light of 905 to 1600 nm used by the LIDAR sensor to measure the distance is absorbed by carbon black, which is widely used as a black pigment for black objects, so that the reflected light becomes weak and difficult to detect. be.
  • an object of the present invention is to provide a dark leather-like sheet that is easily detected by a LIDAR sensor.
  • One aspect of the present invention is a leather-like sheet including a fiber base material and a colored resin layer laminated on the fiber base material, and the colored resin layer includes an intermediate layer and a skin layer laminated on the intermediate layer.
  • the skin layer is a layer containing polyurethane and an infrared reflective black pigment of 3 g / m 2 or more
  • the intermediate layer is a layer containing polyurethane and a black pigment, L * a * b * color.
  • a leather-like sheet having a surface with a lightness L * value of ⁇ 30 in the system.
  • Such a leather-like sheet is easily detected by a LIDAR sensor that emits a pulsed laser beam of 905 to 1600 nm by including a skin layer containing 3 g / m 2 or more of an infrared-reflecting black pigment having a high near-infrared reflectance. It becomes a leather-like sheet with a black skin layer.
  • the epidermis layer colored only with the infrared-reflecting black pigment has a low blackness, and it is difficult to obtain a leather-like sheet having a high blackness.
  • carbon black is added to the epidermis layer to increase the blackness, the reflectance of near infrared rays is significantly reduced.
  • a black pigment to the intermediate layer, a leather-like sheet having a high blackness and a darkly colored surface such that the L * value ⁇ 30 can be obtained. ..
  • the reflectance of the surface of the leather-like sheet to near-infrared rays having a wavelength of 905 nm is 10% or more
  • the reflectance to near-infrared rays having a wavelength of 1550 nm is 10% or more. This is preferable because it is easy to detect.
  • the solar reflectance of the surface of the leather-like sheet in the wavelength region of 250 to 2500 nm is 10% or more on average, the reflectance to near infrared rays is high and the reflectance in the visible light region is also high, so that color is developed. It is preferable because it is easy to obtain a leather-like sheet having good properties.
  • the infrared reflective black pigment has a reflectance of 25% or more for near infrared rays having a wavelength of 905 nm, a reflectance of 50% or more for near infrared rays having a wavelength of 1550 nm, and a transmittance of less than 50% for near infrared rays having a wavelength of 905 nm.
  • CaO-Tio 2 -MnO 2 -based titanium-based black pigment it is preferable because it is easily detected by near-infrared rays in a wide wavelength range of the LIDAR sensor.
  • the epidermis layer contains 0 to 0.5 g / m 2 of carbon black because it does not significantly reduce the reflectance of near infrared rays.
  • the leather-like sheet is used for bags and clothing, for example, to have a surface reflection intensity of 30 or more at a wavelength of 905 nm and a measurement distance of 10 m, which is measured using HORIZON manufactured by Livox Technology Company Limited. In such a dark leather-like sheet, it is preferable because it is easily detected by the LIDAR sensor.
  • FIG. 1 is a schematic cross-sectional view for explaining the layer structure of the silver-like artificial leather of the embodiment.
  • FIG. 2 is a diagram illustrating a method of measuring the reflection intensity of the LIDAR sensor on the surface of the leather-like sheet used in the examples.
  • FIG. 3 is a diagram showing the results when the surface of the leather-like sheet obtained in the example was measured by a LIDAR sensor.
  • the leather-like sheet of the present embodiment is a leather-like sheet including a fiber base material and a colored resin layer laminated on the fiber base material, and the colored resin layer is an intermediate layer and a skin layer laminated on the intermediate layer.
  • the skin layer is a layer containing polyurethane and an infrared reflective black pigment of 3 g / m 2 or more
  • the intermediate layer is a layer containing polyurethane and a black pigment, L * a * b. *
  • a leather-like sheet having a surface with a lightness L * value of ⁇ 30 in a color system.
  • FIG. 1 is a schematic cross-sectional view for explaining the layer structure of the leather-like sheet 10, which is an example of the leather-like sheet of the present embodiment.
  • the leather-like sheet 10 is a colored resin containing a fiber base material 1, a porous layer 2 mainly composed of polyurethane laminated on the fiber base material 1, and an intermediate layer 3 and a skin layer 4 adhered to the intermediate layer 3.
  • the layer 5 is provided with a polyurethane-based adhesive layer 6 for adhering the porous layer 2 and the colored resin layer 5.
  • the leather-like sheet is not limited to such a layer structure, and is a leather-like sheet including a fiber base material and a colored resin layer including an intermediate layer and a skin layer as described above laminated on the fiber base material.
  • the layer structure is not particularly limited.
  • the surface of the epidermis layer may be further provided with a clear layer having a thickness of about 1 to 5 ⁇ m, which is a non-colored transparent resin layer, as necessary, as long as the effects of the present invention are not impaired.
  • the fiber base material a conventionally known artificial leather base material used in the production of artificial leather, such as a non-woven fabric, a woven fabric, a knitted fabric, or a base material impregnated with a polymer elastic material such as polyurethane, or the like.
  • the synthetic leather base material used for synthetic leather is not particularly limited.
  • the polymer elastic body may contain a pigment, if necessary.
  • the thickness of the fiber base material is also not particularly limited, but is preferably, for example, about 0.3 to 3 mm, more preferably about 0.5 to 1.5 mm.
  • the type of fiber forming the fiber base material is not particularly limited, and is not particularly limited, for example, nylon-based fiber, polyester-based fiber, polyolefin-based fiber, polyurethane-based fiber, and the like.
  • the fineness and morphology of the fiber are not particularly limited.
  • the fineness may be a regular fiber having a fineness of more than 1 dtex, or an ultrafine fiber having a fineness of less than 1 dtex.
  • the form of the fiber may be a solid fiber or a fiber having voids such as a hollow fiber or a lotus root-like fiber.
  • the epidermis layer is a polyurethane layer that colors the surface and contains an infrared reflective black pigment of 3 g / m 2 or more.
  • the skin layer is a polyurethane layer containing an infrared reflective black pigment of 3 g / m 2 or more, it becomes a colored polyurethane layer having a high reflectance to near-infrared pulsed laser light, as will be described later.
  • the infrared reflective black pigment has a reflectance of 25% or more for near infrared rays having a wavelength of 905 nm, a reflectance of 50% or more for near infrared rays having a wavelength of 1550 nm, and a transmittance of 50% or less for near infrared rays having a wavelength of 905 nm.
  • the infrared reflective black pigment has a reflectance of 30% or more for near infrared rays having a wavelength of 905 nm, and a transmittance of 30% or less, further 20% or less, and particularly 10% or less for near infrared rays having a wavelength of 905 nm. Is preferable.
  • Specific examples of such infrared-reflecting black pigments include CaO-Tio 2 -MnO 2 titanium-based black pigments (for example, Typake Black SG-103 manufactured by Ishihara Sangyo Co., Ltd.) and Akaho Kasei (Akaho Kasei).
  • Examples thereof include a titanium-based black pigment (Tilack D) manufactured by Co., Ltd., a composite oxide pigment of chromium oxide and iron oxide, and the like.
  • the CaO-Tio 2 -MnO 2 -based titanium black pigment has a reflectance of 30% or more for near-infrared rays having a wavelength of 905 nm, a reflectance of 55% or more for near-infrared rays having a wavelength of 1550 nm, and a near-infrared ray having a wavelength of 905 nm.
  • the transmittance for the infrared ray is 10% or less.
  • a CaO-Tio 2 -MnO 2 -based titanium-based black pigment it is manufactured by a method in which a calcium compound, a titanium compound, and a manganese compound are mixed by a wet pulverization method and fired at a temperature higher than 1100 ° C. Will be done.
  • a CaO-Tio 2 -MnO 2 -based titanium-based black pigment preferably has a perovskite phase as a main phase and a BET specific surface area of 1.0 m 2 / g or more and less than 3.0 m 2 / g.
  • the epidermis layer contains 3 g / m 2 or more of an infrared reflective black pigment, preferably 3 to 5 g / m 2 .
  • an infrared reflective black pigment preferably 3 to 5 g / m 2 .
  • the thickness of the epidermis layer is not particularly limited as long as it contains 3 g / m 2 or more of the infrared reflective black pigment, but is preferably 10 ⁇ m or more, more preferably 20 to 30 ⁇ m. If the epidermis layer is too thin, it tends to be difficult to contain 3 g / m 2 or more of the infrared reflective black pigment.
  • the content ratio of the infrared reflective black pigment in the skin layer is not particularly limited as long as the skin layer contains 3 g / m 2 or more of the infrared reflective black pigment, but is 10% by mass or more, further, 15% by mass or more, particularly. Is preferably 20% by mass or more. If the content ratio of the infrared reflective black pigment is too low, it becomes difficult to contain 3 g / m 2 or more of the infrared reflective black pigment, and if it is too high, the blackness tends to be low and the costability tends to decrease. be.
  • the skin layer contains 0 to 0.5 g / m 2 of carbon black, and further 0 to 0, depending on the type of carbon black, as long as it does not contain carbon black or does not impair the effect of the present invention. . It may be contained in the range of 1 g / m 2 .
  • the carbon black preferentially absorbs the near infrared rays radiated to the surface of the obtained leather-like sheet, so that the near infrared rays are reflected. The rate tends to be low and the detectability by the LIDAR sensor tends to decrease.
  • the epidermis layer may contain other pigments other than carbon black as long as the effects of the present invention are not impaired.
  • Other pigments are not particularly limited as long as the absorption rate of near infrared rays in the wavelength range of 905 to 1600 nm is not too high, but specifically, for example, anthraquinone-based pigments, diketopyrrolopyrrole-based pigments, perylene black and the like. Examples include perylene-based pigments.
  • perylene black has a transmittance of 60% or more for near infrared rays having a wavelength of 905 nm, when used alone, the reflectance of near infrared rays is low, so that the detectability by the LIDAR sensor is low. In addition, the color development of dark colors is low.
  • the average dispersed particle size in the colored resin layer of the infrared reflective black pigment is not particularly limited, but is preferably 1 to 10 ⁇ m, more preferably 1.5 to 8 ⁇ m.
  • the average dispersed particle size of the infrared-reflecting black pigment is in such a range, diffuse reflection of light on the surface of the infrared-reflecting black pigment particles is likely to be suppressed, and a black-based colored resin layer having a high degree of blackness is likely to be formed. Tend to be.
  • the average dispersed particle size of the infrared-reflecting black pigment is too small, light tends to be diffusely reflected on the surface of the infrared-reflecting black pigment particles, so that the surface of the leather-like sheet tends to develop a reddish color. be. Further, when the average dispersed particle size of the infrared reflective black pigment is too large, the mechanical properties of the film of the colored resin layer are deteriorated, so that the abrasion resistance of the surface of the leather-like sheet tends to be lowered. ..
  • the intermediate layer is a layer containing polyurethane and a black pigment, and is colored in a deep color.
  • the intermediate layer is a polyurethane layer that is deeply colored by being a layer containing a black pigment.
  • Such an intermediate layer is a layer for adjusting the color visible from the surface to be darker without adding a large amount of carbon black to the epidermis layer.
  • black pigment contained in the intermediate layer examples include carbon black such as furnace black, channel black, and acetylene black, infrared reflective black pigment, and composite oxide black pigment.
  • carbon black is preferable because it is easy to obtain a dark surface.
  • the infrared reflective black pigment is preferable from the viewpoint of further increasing the reflectance of near infrared rays.
  • the intermediate layer may contain other pigments other than the black pigment for toning, as long as the effect of the present invention is not impaired.
  • Other pigments are not particularly limited, and specific examples thereof include anthraquinone-based pigments, diketopyrrolopyrrole-based pigments, and perylene-based pigments.
  • the intermediate layer contains carbon black as a black pigment, it has a surface of L * value ⁇ 30 that it contains 0.2 g / m 2 or more of carbon black, and further 0.5 to 5 g / m 2 . It is preferable because it is easy to obtain a dark leather-like sheet.
  • the intermediate layer contains an infrared reflective black pigment as a black pigment
  • the surface of the surface having an L * value of ⁇ 30 is that the intermediate layer contains 2 g / m 2 or more of the infrared reflective black pigment and further 2 to 5 g / m 2 . It is preferable because it is easy to obtain a dark-colored leather-like sheet having.
  • the thickness of the intermediate layer is not particularly limited as long as the surface of the leather-like sheet can be adjusted to the surface having a brightness L * value ⁇ 30, but is preferably 10 to 50 ⁇ m, more preferably 20 to 30 ⁇ m. If the intermediate layer is too thin, it tends to be difficult to adjust to a dark surface such as L * value ⁇ 30.
  • the content ratio of the black pigment in the intermediate layer is not particularly limited as long as the surface of the leather-like sheet can be adjusted to the surface of L * value ⁇ 30.
  • carbon black is contained as the black pigment, it is preferable to contain carbon black in an amount of 2% by mass or more, more preferably 2 to 10% by mass.
  • the infrared reflective black pigment is contained as the black pigment, it is preferable that the infrared reflective black pigment is contained in an amount of 10% by mass or more, more preferably 10 to 20% by mass. If the content of the black pigment is too small, it tends to be difficult to obtain a dark surface such as L * value ⁇ 30.
  • Polyurethane for forming the intermediate layer, the epidermis layer, and the porous layer is obtained by reacting a urethane raw material containing a polymer polyol, an organic polyisocyanate, and a chain extender.
  • Polyurethane is prepared as a melt, an organic solvent solution (eg, a solution of an organic solvent such as dimethylformamide, methylethylketone, acetone, toluene), an aqueous dispersion, or an emulsion during the production of a leather-like sheet.
  • high polymer polyol examples include polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and polymethyltetramethylene glycol; polyhexamethylene carbonate diol, and poly (3-methyl-1,5-).
  • Polyester-based polyols such as pentylene carbonate) diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol; polyethylene adipate diol, polybutylene adipate diol, polypropylene adipate diol, polybutylene sebacate diol, polyhexamethylene adipate diol, poly ( Examples thereof include polyester-based polyols such as 3-methyl-1,5-pentylene adipate) diol, poly (3-methyl-1,5-pentylene sebacate) diol, and polycaprolactone diol, or copolymers thereof. .. These may be used alone or in combination of two or more.
  • organic polyisocyanate examples include aromatic diisocyanates such as 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate.
  • Modified diisocyanates examples thereof include aliphatic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and non-yellowing diisocyanates such as alicyclic diisocyanate.
  • a polyfunctional isocyanate such as a trifunctional isocyanate or a tetrafunctional isocyanate may be used in combination. These may be used alone or in combination of two or more.
  • chain extender examples include diamines such as hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, adipic acid dihydrazide, and isophthalic acid dihydrazide.
  • diamines such as hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, nonamethylenediamine, xylylenediamine, isophoronediamine, piperazine and its derivatives, adipic acid dihydrazide, and isophthalic acid dihydrazide.
  • triamines such as diaminetriamines; tetramines such as triethylenetetramine; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis ( ⁇ -hydroxyethoxy) benzene, 1
  • Diamines such as 4-cyclohexanediol
  • Triols such as trimethylolpropane
  • Tetraols such as pentaerythritol
  • Amino alcohols such as aminoethyl alcohol and aminopropyl alcohol.
  • monoamines such as ethylamine, propylamine, and butylamine; carboxyl group-containing monoamine compounds such as 4-aminobutanoic acid and 6-aminohexanoic acid; methanol, ethanol, propanol, butanol, etc.
  • Monools may be used in combination.
  • Polyurethane for forming a porous layer is formed, for example, by applying a wet-solidifying polyurethane solution to the surface of a fiber substrate and then immersing it in an aqueous coagulation bath to coagulate the porous polyurethane. .. Further, the porous layer may be infiltrated into the porous layer for the purpose of imparting morphological stability to the fiber base material.
  • the fiber base material is impregnated with the polyurethane solution in advance, further coated with the polyurethane solution, and then immersed in an aqueous coagulation bath to coagulate the inside of the fiber base material.
  • the thickness of the porous layer is not particularly limited, but is preferably, for example, about 100 to 600 ⁇ m, more preferably about 200 to 400 ⁇ m.
  • a polyurethane film for forming the skin layer is formed on the release paper. Then, by forming the polyurethane film for forming the intermediate layer on the polyurethane film of the epidermis layer, the colored resin layer including the intermediate layer and the epidermis layer laminated on the intermediate layer is formed.
  • the colored resin layer may further include a layer other than the intermediate layer in the layer below the epidermis layer.
  • an adhesive is applied to the colored resin layer, and the solvent is completely or incompletely removed and dried.
  • the adhesive laminated on the colored resin layer formed on the release paper is bonded to the surface of the porous layer and pressed, and then the adhesive is cured to form the porous layer via the adhesive layer. Adhere to the colored resin layer. Then, by peeling the release paper from the surface of the colored resin layer, a leather-like sheet having a fiber base material and a colored resin layer laminated on the fiber base material can be obtained.
  • the leather-like sheet of the present embodiment has a colored resin layer containing a skin layer containing an infrared reflective black pigment and an intermediate layer containing a black pigment as described above, thereby forming an L * a * b * color system. * The leather-like sheet is colored so as to have a surface with a value of ⁇ 30.
  • coloring so as to have a surface with a lightness L * value ⁇ 30 means that the dark colored surface, which is the design surface of the leather-like sheet, is a spectrophotometer. It means that the brightness L * value ⁇ 30 calculated from the coordinate values of the L * a * b * color system obtained by measuring the color using.
  • the brightness of the dark surface is preferably L * value ⁇ 30, and more preferably L * value ⁇ 25.
  • the leather-like sheet of the present embodiment is provided with a skin layer containing an infrared-reflecting black pigment as described above, whereby a leather-like sheet having a high reflectance to near-infrared rays can be obtained. As a result, a dark leather-like sheet that is easily detected by the LIDAR sensor can be obtained.
  • the reflectance of the surface of such a leather-like sheet with a brightness L * value ⁇ 30 to near infrared rays it is preferable that the reflectance to near infrared rays having a wavelength of 905 nm is 10% or more, more preferably 15% or more. Further, it is preferable that the reflectance for near infrared rays having a wavelength of 1550 nm is 10% or more, more preferably 15% or more.
  • the solar reflectance in the wavelength region of 250 to 2500 nm on the surface of the leather-like sheet is preferably 10% or more, more preferably 15% or more.
  • the solar reflectance is in such a range, it is preferable because the reflectance to near infrared rays is high and a leather-like sheet having a lightness L * value of ⁇ 30 with good color development can be more easily obtained.
  • the leather-like sheet of the present embodiment described above is preferably used as a silver-like leather-like sheet similar to natural leather, which is used as a skin material for bags, clothing, shoes, and the like.
  • a leather-like sheet is used for the back surface material that covers many areas of the wearer's body, and the back bag such as a school bag is used, or as a material for clothing.
  • the back bag such as a school bag is used, or as a material for clothing.
  • it is preferably used as a silver-like leather-like sheet that is detected with high accuracy by the LIDAR sensor.
  • Such a leather-like sheet is, for example, measured from the skin layer side using a LIDAR sensor HORIZON manufactured by Livox Technology Company Limited, at a wavelength of 905 nm and a reflection intensity of 40 or more at a measurement distance of 10 m, and further at 50 or more. This is preferable because it is easily detected by a LIDAR sensor, for example, which is mounted on a car as a safety device.
  • Example 1 After melt-spinning a sea-island type composite fiber containing 45 parts by mass (sea component) of 6-nylon (sea component) and 55 parts by mass (island component) of polystyrene, stretching it three times, applying a fiber oil agent, and mechanically crimping it. , Dry. The obtained crimped fibers were cut to 51 mm to form 3 decitex staples to form a web. Then, needle punching of about 500 punches / cm 2 was performed alternately from both sides of the web to obtain an entangled nonwoven fabric. The basis weight of this entangled nonwoven fabric was 350 g / m 2 , and the apparent specific gravity was 0.17.
  • This entangled nonwoven fabric was treated with a 4% aqueous solution of polyvinyl alcohol, compressed and fixed to a thickness of about 1.3 mm, and the surface was buffed and smoothed. Then, it was impregnated with a dimethylformamide (hereinafter referred to as DMF) solution of polyurethane mainly composed of polyester-based polyurethane having a concentration of 13%. Further, the same polyurethane solution was applied to the surface in an amount of 100 g / m 2 in solid content, and then immersed in a mixed solution of DMF / water to make the polyurethane porous and wet-coagulate.
  • DMF dimethylformamide
  • the island component was eluted and removed in hot toluene to convert the sea-island type composite fiber into a hollow fiber.
  • a fiber base material having a porous layer permeated into the surface layer laminated was obtained.
  • the thickness of the porous layer was 300 ⁇ m.
  • a black vehicle containing 100 parts by mass of a 22% DMF solution of non-yellowing polycarbonate-based polyurethane and 20% by mass of an infrared reflective black pigment (titanium-based black pigment) on a release paper (R-70 manufactured by Lintec Co., Ltd.).
  • a polyurethane composition solution containing 30 parts by mass and 30 parts by mass of DMF was applied at 100 g / m 2 to a thickness of about 20 ⁇ m after drying, and dried at 120 ° C. for 2 minutes to form a black skin layer.
  • the titanium-based black pigment has a reflectance of 30.1% at 905 nm, a reflectance of 57.1% at 1550 nm, and a transmittance of 10% or less for near infrared rays having a wavelength of 905 nm.
  • Typake Black SG103 manufactured by Ishihara Sangyo Co., Ltd. which is a 2 -MnO 2 black pigment, was used.
  • the obtained skin layer did not contain carbon black, and the amount of the titanium-based black pigment contained in the skin layer was 4.8 g / m 2 .
  • the content of the titanium-based black pigment in the epidermis layer was 20% by mass.
  • a black intermediate layer was formed by applying 120 g / m 2 of the polyurethane composition solution containing the mixture to a thickness of about 20 ⁇ m after drying and drying at 120 ° C. for 2 minutes.
  • the furness black has a reflectance of about 5% at 905 nm, a reflectance of about 6% at 1550 nm, and a transmittance of 5% or less for near infrared rays having a wavelength of 905 nm.
  • the amount of carbon black per unit area of the obtained intermediate layer was 0.6 g / m 2 .
  • the carbon black content of the intermediate layer was 3% by mass.
  • a polyurethane-based adhesive solution was applied to the surface of the intermediate layer formed on the release paper, and the solution was dried at 120 ° C. for 2 minutes to evaporate the solvent to form an adhesive layer.
  • the adhesive layer on the release paper was bonded to the porous layer laminated on the fiber base material to produce a laminated intermediate.
  • the laminated intermediate was crimped by pressing with a roll having a surface temperature of 75 ° C. provided with a clearance.
  • the release paper was peeled off to obtain a leather-like sheet which is a silver-like artificial leather having a black surface.
  • an ultraviolet-visible near-infrared spectrophotometer (V-670 manufactured by Nippon Denshoku Kogyo Co., Ltd.) was used, and the sample was placed in a measurement cell as a powder. , The spectral reflectance and transmittance in the range of 300 nm to 2500 nm were measured.
  • FIG. 3 is a diagram showing the results when the reflection intensity of near infrared rays on the surface of the leather-like sheet is measured by the LIDAR sensor.
  • (A) is the figure which measured the surface of the leather-like sheet of Example 1
  • (b) is the figure which measured the surface of the leather-like sheet of Comparative Example 1.
  • the particle diameter when the volume accumulation frequency became 50% was defined as the dispersed particle diameter (D50).
  • the above measurement was performed at any 5 points of the leather-like sheet, and the average value of the dispersed particle diameters (D50) at the 5 points was taken as the average dispersed particle diameter.
  • Example 2 In Example 1, the skin layer containing the infrared reflective black pigment of 4.8 g / m 2 was replaced with the skin layer containing the infrared reflective black pigment of 3.4 g / m 2 , except that the skin layer was changed to the same as in Example 1. Artificial leather was obtained and evaluated in the same manner. The results are shown in Table 1.
  • Example 3 In Example 1, the same procedure as in Example 1 was carried out except that the intermediate layer containing 0.6 g / m 2 of carbon black was replaced with an intermediate layer containing 3.4 g / m 2 of infrared reflective black pigment. Artificial leather was obtained and evaluated. The results are shown in Table 1.
  • Example 4 In Example 3, instead of the epidermis layer containing 4.8 g / m 2 of infrared reflective black pigment, the epidermis containing 4.8 g / m 2 of infrared reflective black pigment and 0.5 g / m 2 of carbon black. Artificial leather was obtained and evaluated in the same manner as in Example 1 except that the layer was changed. The results are shown in Table 1.
  • Example 1 In Example 1, instead of the skin layer containing 4.8 g / m 2 of the infrared-reflecting black pigment, the skin layer containing 3.4 g / m 2 of carbon black is changed to adjust the brightness to a black color that is close to that of the skin layer. Artificial leather was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • Example 2 Artificial leather was obtained and evaluated in the same manner as in Example 1 except that the intermediate layer containing 0.6 g / m 2 of carbon black was replaced with an intermediate layer containing no pigment. The results are shown in Table 1.
  • Example 3 In Example 1, instead of the epidermis layer containing 4.8 g / m 2 of infrared reflective black pigment, the epidermis containing 1.9 g / m 2 of infrared reflective black pigment and 1.9 g / m 2 of carbon black. Artificial leather was obtained and evaluated in the same manner as in Example 1 except that the layer was changed. The results are shown in Table 1.
  • Example 4 In Example 1, instead of the epidermis layer containing 4.8 g / m 2 of infrared reflective black pigment, the epidermis containing 2.9 g / m 2 of infrared reflective black pigment and 1.9 g / m 2 of carbon black. Artificial leather was obtained and evaluated in the same manner as in Example 1 except that the layer was changed. The results are shown in Table 1.
  • Example 5 In Example 1, instead of the epidermis layer containing 4.8 g / m 2 of infrared reflective black pigment, the epidermis containing 4.8 g / m 2 of infrared reflective black pigment and 0.6 g / m 2 of carbon black. Artificial leather was obtained and evaluated in the same manner as in Example 1 except that the layer was changed to an intermediate layer containing no pigment instead of the intermediate layer containing 0.6 g / m 2 of carbon black. The results are shown in Table 1.
  • Example 6 artificial leather was obtained and evaluated in the same manner as in Example 1 except that the epidermis layer and the intermediate layer were exchanged. The results are shown in Table 1.
  • Example 7 In Example 1, the skin layer containing 4.8 g / m 2 of the infrared reflective black pigment was replaced with the skin layer containing 4.8 g / m 2 of the perylene-based black pigment. Artificial leather was obtained and evaluated in the same manner.
  • perylene-based black pigment perylene black (Paliogen Black L0084) having a transmittance of 65% or more for near infrared rays having a wavelength of 905 nm was used. The results are shown in Table 1.
  • Example 8 In Example 3, the skin layer containing 4.8 g / m 2 of the infrared reflective black pigment was replaced with the skin layer containing 4.8 g / m 2 of the perylene-based black pigment (Paliogen Black L0084). Artificial leather was obtained and evaluated in the same manner as in Example 1. The results are shown in Table 1.
  • the leather-like sheet which is the artificial leather of Examples 1 to 4 in which the skin layer contains an infrared reflective black pigment of 3 g / m 2 or more and the intermediate layer contains the black pigment is All were leather-like sheets having a dark surface with an L * value of ⁇ 30 and having high detectability by the LIDAR sensor.
  • the leather-like sheets of Comparative Examples 1, 3, 4, and 6 in which the skin layer did not contain an infrared reflective black pigment of 3 g / m 2 or more were not sufficiently detectable by the LIDAR sensor.
  • the leather-like sheet which is the artificial leather of Comparative Example 2 in which the skin layer contains an infrared reflective black pigment of 3 g / m 2 or more but the intermediate layer does not contain the black pigment, has a darkness of L * value ⁇ 30. No colored surface was obtained.
  • the leather-like sheet which is the artificial leather of Comparative Example 5, in which the skin layer contains carbon black together with the infrared reflective black pigment of 3 g / m 2 or more and the intermediate layer does not contain the black pigment, has an L * value ⁇ . Although a dark surface of 30 was obtained, the detectability by the LIDAR sensor was not sufficient due to the absorption of near infrared rays by carbon black.
  • the leather-like sheet which is the artificial leather of Comparative Example 7 in which the epidermis layer contains a perylene-based black pigment and the intermediate layer is a layer containing a black pigment, has a dark surface with an L * value of ⁇ 30.
  • the detectability by the LIDAR sensor was not sufficient because the epidermis layer easily transmits near infrared rays.
  • the leather-like sheet of Comparative Example 8 which is a layer in which the epidermal layer contains a perylene-based black pigment and the intermediate layer contains an infrared-reflecting black pigment, had good detectability by a LIDAR sensor, but had an L * value. No dark surface of ⁇ 30 was obtained.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)
PCT/JP2021/041913 2020-11-17 2021-11-15 皮革様シート、及びそれを背表材として用いた背負い鞄 Ceased WO2022107720A1 (ja)

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CN202180076428.2A CN116438058B (zh) 2020-11-17 2021-11-15 皮革状片及使用了该皮革状片作为背面表面材料的背包
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JP2022186399A (ja) * 2021-06-04 2022-12-15 株式会社クラレ 皮革様シート
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JP2022186399A (ja) * 2021-06-04 2022-12-15 株式会社クラレ 皮革様シート
JP7610469B2 (ja) 2021-06-04 2025-01-08 株式会社クラレ 皮革様シート
US20230400610A1 (en) * 2022-06-08 2023-12-14 Toyota Motor Engineering & Manufacturing North America, Inc. Lidar reflective fabric
US12169294B2 (en) * 2022-06-08 2024-12-17 Toyota Motor Engineering & Manufacturing North America, Inc. LiDAR reflective fabric

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EP4249671A4 (en) 2024-10-16
CN116438058A (zh) 2023-07-14
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