WO2018123290A1 - Synthetic leather - Google Patents

Synthetic leather Download PDF

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Publication number
WO2018123290A1
WO2018123290A1 PCT/JP2017/040468 JP2017040468W WO2018123290A1 WO 2018123290 A1 WO2018123290 A1 WO 2018123290A1 JP 2017040468 W JP2017040468 W JP 2017040468W WO 2018123290 A1 WO2018123290 A1 WO 2018123290A1
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WO
WIPO (PCT)
Prior art keywords
fiber
synthetic leather
layer
flame retardant
base fabric
Prior art date
Application number
PCT/JP2017/040468
Other languages
French (fr)
Japanese (ja)
Inventor
賢治 久保
倫行 石山
Original Assignee
共和レザー株式会社
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 共和レザー株式会社 filed Critical 共和レザー株式会社
Priority to CN201780076655.9A priority Critical patent/CN110073053B/en
Priority to US16/469,249 priority patent/US20190382953A1/en
Priority to JP2018558877A priority patent/JP6895458B2/en
Publication of WO2018123290A1 publication Critical patent/WO2018123290A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—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
    • D06N3/0009—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 knitted fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—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
    • 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
    • D06N3/0015—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
    • D06N3/0034—Polyamide fibres
    • 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
    • D06N3/0015—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
    • D06N3/0038—Polyolefin fibres
    • D—TEXTILES; PAPER
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    • 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
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    • 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
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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
    • D06N3/0056—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
    • D06N3/0059—Organic ingredients with special effects, e.g. oil- or water-repellent, antimicrobial, flame-resistant, magnetic, bactericidal, odour-influencing agents; perfumes
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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
    • D06N3/0056—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
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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
    • D06N3/0077—Embossing; Pressing of the surface; Tumbling and crumbling; Cracking; Cooling; Heating, e.g. mirror finish
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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
    • D06N3/0095—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
    • D—TEXTILES; PAPER
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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
    • D06N3/0095—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
    • 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
    • D06N3/02—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with cellulose derivatives
    • 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
    • D06N3/04—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
    • D06N3/042—Acrylic polymers
    • D—TEXTILES; PAPER
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    • 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
    • D06N3/04—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
    • D06N3/06—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 polyvinylchloride or its copolymerisation products
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
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    • 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
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
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    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0218—Vinyl resin fibres
    • D06N2201/0236—Vinyl halide, e.g. PVC, PVDC, PVF, PVDF
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    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/02—Synthetic macromolecular fibres
    • D06N2201/0263—Polyamide fibres
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    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/04—Vegetal fibres
    • D06N2201/042—Cellulose fibres, e.g. cotton
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    • D06N2201/00—Chemical constitution of the fibres, threads or yarns
    • D06N2201/08—Inorganic fibres
    • D06N2201/087—Carbon fibres
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    • D06N2209/00—Properties of the materials
    • D06N2209/06—Properties of the materials having thermal properties
    • D06N2209/067—Flame resistant, fire resistant

Definitions

  • This disclosure relates to synthetic leather.
  • Synthetic leather having excellent durability is often used in place of natural leather and fibrous sheets for members, clothing covering materials, clothing lining materials, wall covering materials, and the like.
  • synthetic leather used for aircraft interior parts and automobile interior parts needs to be lightweight and durable and have good fire resistance.
  • Synthetic leather generally has a flexible resin layer for adjusting moderate elasticity on the surface of a fibrous sheet such as a base fabric, and leather-like, from the viewpoint of good dimensional stability and processability. And has a skin layer excellent in wear resistance.
  • the applicant of the present application has a double-sided knitted structure using a yarn containing a flame retardant fiber having a limiting oxygen index (LOI value) of 25 or more and a cellulosic fiber, and has a mass of 150 g / m 2 to 250 g. / m a knitting member 2, the LOI value of knitting made body on the base fabric for artificial leather is 25 or more, water-based polyurethane adhesive layer, and has proposed a synthetic leather having a water-based polyurethane skin layer in this order (Japanese (See JP 2013-0721141).
  • LOI value limiting oxygen index
  • the synthetic leather described in Japanese Patent Application Laid-Open No. 2006-77349 is inferior in finish when the thickness and strength of the woven fabric and nonwoven fabric used for the base fabric are not sufficient, for example, when used for a seat seat or the like. There's a problem. Furthermore, at the time of manufacture, the base fabric is impregnated with a flame retardant, etc., and then dried and adhered to the resin layer. Therefore, the manufacturing process is complicated, and depending on the flame retardant used, toxic gas or fuming factor at the time of combustion There was a problem that it could be both.
  • the synthetic leather described in JP2013-0721141 has a feeling close to that of natural leather, has good durability, processability, and flame retardancy, and suppresses generation of toxic gas even when burned.
  • An object of one embodiment of the present invention is to provide a synthetic leather that has good flame retardancy and has reduced smoke generation during combustion.
  • the flame retardant fiber is aramid fiber, meta-aramid fiber, polyphenylene sulfide fiber, acrylic fiber, vinyl chloride fiber, polyclar fiber, vinylidene chloride fiber, acrylic-vinyl chloride copolymer fiber, and acrylic-vinylidene chloride.
  • the carbon fiber content is 20% by mass to 40% by mass with respect to the total mass of the yarn constituting the knitted body, and the cellulosic fiber content is 25 with respect to the total mass of the yarn constituting the knitted body.
  • the total content of the flame retardant fiber and the carbon fiber is greater than the content of the cellulosic fiber by 1% to 45% by mass, and is any one of [1] to [3] Synthetic leather.
  • a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
  • the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is. Constituent elements indicated using the same reference numerals in the drawings mean the same constituent elements.
  • the upper limit value or lower limit value described in a numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other steps.
  • the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
  • the synthetic leather of the present disclosure is a knitted body of yarn containing a flame retardant fiber having a LOI value of 25 or more, a cellulosic fiber, and a carbon fiber, and a base fabric having a LOI value of 25 or more, An adhesive layer including a flame retardant provided on at least one surface; and a skin layer provided on a surface of the adhesive layer opposite to the surface on the base fabric side.
  • the synthetic leather base fabric refers to a base material that forms each layer of the synthetic leather and is a fabric selected from a knitted fabric, a woven fabric, a non-woven fabric, and the like.
  • the base fabric in the present disclosure is a knitted body, that is, a knitted fabric formed by knitting fibers.
  • the base fabric used for the synthetic leather of the present disclosure is a yarn including a flame retardant fiber having a LOI value of 25 or more (hereinafter sometimes referred to as “flame retardant fiber”), a cellulosic fiber, and a carbon fiber.
  • the LOI value of the base fabric itself which is a knitted body and is a knitted body, is 25 or more.
  • the knitted body used for the base fabric is knitted using yarns containing at least the three kinds of different fibers described above.
  • the limiting oxygen index (LOI value) indicates the oxygen concentration necessary for an object to continue to burn, and is measured by the method described in JIS K7201 (2006) (ASTM D2863). Usually, since the oxygen concentration in the air is about 21.2%, if the LOI value is 25 or more, it can be said that the flame retardancy is good.
  • the base fabric is a base fabric for synthetic leather used for vehicle interior materials, etc.
  • the yarn used for knitting the knitted body has a thickness of about 16 to 40.
  • count means “cotton count”
  • the weight is 1 pound (1 Lb: 0.452525937 kg) and the length is 840 yards (1yard: 768.096 m). It represents that.
  • a thread that weighs 1 pound and is 1680 yards long is called second. Therefore, it shows that it is a thick fiber, so that a numerical value of a count is small.
  • the flame retardant fiber used for the base fabric is not particularly limited as long as the LOI value is 25 or more.
  • Incombustible fiber is not non-combustible fiber.
  • a flame retardant synthetic fiber is preferable from the viewpoint that a knitted body having a flexible and volume feeling can be formed.
  • the fiber which carried out the flame-retardant process with respect to the fiber which is not a flame-retardant fiber, and made LOI value 25 or more can be used as a flame-retardant fiber in a base fabric.
  • Examples of the fiber having a LOI value of 25 or more by flame retardant processing include flame retardant polynosic fiber, flame retardant polyester fiber, flame retardant acrylic fiber, and flame retardant rayon fiber. From the viewpoint of ease of production and suppression of smoke generation, it is preferable to use a flame retardant fiber in which the material itself constituting the fiber is flame retardant.
  • the flame retardant fiber in the present disclosure has a LOI value of 25 or more.
  • the LOI value of the flame retardant fiber is preferably 26 or more, more preferably 28 or more.
  • the thickness of the yarn containing flame retardant fibers used for knitting a knitted body is about 16th to 40th. It is preferable that
  • Cellulose fiber There is no restriction
  • the LOI value of the entire base fabric as the knitted body is 25 or more while taking advantage of the characteristics of the cellulosic fiber by combining the flame retardant fiber described above and the carbon fiber described later into a knitted body. Is done.
  • the cellulosic fiber is carbonized at the time of combustion, and the burning rate of the knitted body can be delayed.
  • Carbon fiber is obtained by heating and carbonizing a precursor of carbon fiber such as organic fiber, and refers to a fiber in which 90% by mass or more is composed of carbon with respect to the total mass of the fiber.
  • carbon fiber used for the production of the synthetic leather base fabric of the present disclosure.
  • carbon fiber contains at least 1 sort (s) chosen from the PAN (polyacrylonitrile) type
  • the base fabric is knitted using, as carbon fibers, a yarn spun containing at least one selected from polyacrylonitrile (PAN) fibers, pitch fibers, and phenol fibers.
  • PAN polyacrylonitrile
  • Carbon fiber mainly contains hydrogen and oxygen derived from the raw material resin as elements other than carbon.
  • carbon fiber does not contain elements such as phosphorus, it is difficult to burn, and even when burned, it produces very little smoke.
  • carbon fiber has high thermal conductivity, it is possible to effectively suppress the spread of fire at the time of ignition when the base fabric includes carbon fiber.
  • each fiber is contained in the yarn containing at least the above-mentioned flame retardant fiber, cellulosic fiber, and carbon fiber used for knitting the base fabric.
  • it may be knitted using three types of yarns including a flame retardant fiber, a cellulose fiber, and a carbon fiber, and a mixed yarn including two of the three types of fibers.
  • the yarn containing the remaining one type may be knitted, or may be knitted using the blended yarn containing the three types of fibers described above.
  • the cellulosic fiber is blended with the flame retardant fiber and carbon fiber described above.
  • the yarn used for producing the knitted product is a blended yarn of flame retardant fiber and cellulosic fiber, or a blend of carbon fiber and cellulosic fiber. It is preferably a blended yarn selected from yarns and blended yarns of flame retardant fibers, cellulosic fibers, and carbon fibers, and in particular, blended yarns of flame retardant fibers, cellulosic fibers, and carbon fibers.
  • the LOI value of the obtained knitted body can be 25 or more.
  • the flame retardant fiber, cellulosic fiber, and carbon fiber content in the base fabric is appropriately adjusted within a range where the LOI value of the resulting knitted fabric can be 25 or more.
  • the base fabric used for the synthetic leather of the present disclosure is a knitted body knitted with a yarn containing flame retardant fibers, cellulosic fibers, and carbon fibers, and the LOI value of the knitted body itself is 25 or more. is there.
  • the carbon fiber content is 20% by mass to 40% by mass with respect to the total mass of the yarn constituting the knitted body, and the cellulosic fiber content is 25% by mass with respect to the total mass of the yarn constituting the knitted body. It is preferable that the total content of the flame retardant fiber and the carbon fiber is larger than the content of the cellulosic fiber.
  • the total content of flame retardant fibers and carbon fibers in the knitted fabric is preferably more than 50% by mass, and the yarn constituting the knitted fabric It is more preferable that the ratio of the total amount of the flame retardant fiber and the carbon fiber with respect to the total mass is 60 mass% or more and 90 mass% or less. Further, the content of the carbon fiber with respect to the total mass of the yarn constituting the knitted body is preferably 20% by mass to 40% by mass and more preferably 30% by mass to 40% by mass from the viewpoint of the smoke generation suppressing effect. preferable.
  • the content of the cellulosic fibers with respect to the total mass of the yarn constituting the knitted body is preferably 25% by mass to 45% by mass, More preferably, the content is 25% by mass to 40% by mass.
  • the knitted body preferably has a double-sided knitted structure.
  • the texture and elasticity of the synthetic leather resulting from the base fabric become better.
  • a yarn used when knitting a knitted body having a double-sided knitted structure with a yarn containing a flame retardant fiber, a cellulosic fiber, and a carbon fiber from the viewpoint of the elasticity and strength of the resulting base fabric, a thickness of 20
  • the thus obtained knitted body is preferably mass is in the range of 150g / m 2 ⁇ 400g / m 2, and more preferably in the range of 175g / m 2 ⁇ 350g / m 2.
  • the structure of the knitted body is not particularly limited, and it is a mixed spun yarn obtained by twisting flame retardant fibers, cellulosic fibers and carbon fibers, and may be a uniform knitted body. It consists of yarns made of flame retardant fibers and cellulosic fibers. It is a double-sided knitted structure that uses yarn and carbon fiber yarn separately, and is a knitted body that is structured so that mainly flame-retardant fibers and carbon-based fibers are exposed on one side, and cellulose fibers are mainly exposed on the other side. May be.
  • the yarn suitable for knitting the base fabric is a twisted yarn (mixed yarn), and also from the viewpoint of improving the flame retardancy effect.
  • a blended yarn containing flame retardant fiber, cellulosic fiber and carbon fiber is preferred. That is, when a double-sided knitted structure using a blended yarn containing flame retardant fibers, cellulosic fibers, and carbon fibers, a good texture resulting from the cellulosic fibers can be obtained, and it is difficult to burn during combustion.
  • Preferable embodiments of the double-sided knitting structure include a mocrodi knitting that is a dense double-sided knitting, a changeable structure of double-sided knitting, and a pontoroma knitting that is a structure in which double-sided knitting and bag knitting are alternately repeated.
  • a mocrodi knitting that is a dense double-sided knitting
  • a changeable structure of double-sided knitting and a pontoroma knitting that is a structure in which double-sided knitting and bag knitting are alternately repeated.
  • a knitted body having a mocrodi knitted structure since it is double-sided knitting and high gauge, it is dense, has an appearance similar to a woven fabric, has a feeling of thickness, and has flexibility unique to the knitted body Combines elasticity.
  • the base fabric is a knitted body of mocrodi knitting
  • the gauge indicates the number of meshes per unit length, and the high gauge indicates a high-density knitted body having a large number of meshes per unit length.
  • a knitted body in which the first yarn is mainly exposed on one side and the second yarn is mainly exposed on the other surface can be formed. It is difficult to expose the surface of mainly cellulose fibers, by exposing the yarn made of fuel fiber and carbon fiber and using it on the surface side, and making the surface where the flammable cellulosic fiber is exposed as the back surface. It can be set as the knitted body protected by the layer which consists of a fuel fiber and a carbon-type fiber.
  • blended yarns having the same composition may be used, or two types of blended yarns having different blending rates may be used.
  • the combined use of the three kinds of fibers improves the flame retardancy of the entire base fabric and effectively suppresses smoke generation during combustion.
  • a flame retardant fiber As a base fabric, a flame retardant fiber, a cellulosic fiber that is a natural fiber and excellent in breathability and texture, and a carbon fiber that is high in strength and flame retardant, has high thermal conductivity, and does not emit smoke even when heated.
  • the synthetic leather according to the present disclosure further includes a synthetic leather having good flame retardancy due to a combination of the flame retardance of the base fabric and the flame retardance of the adhesive layer because the adhesive layer contains a flame retardant as described later. I think that will be.
  • the synthetic leather of the present disclosure is formed using this base fabric because the flame resistance of the base fabric is good, smoke generation during combustion is suppressed, and it is excellent in strength and elasticity, and is flexible.
  • the synthetic leather is excellent in strength and processability.
  • the base fabric which is a knitted body may have raising at least on one side. Brushed can be formed by a conventional method. By bringing the surface of the base fabric having the raised portions into contact with an adhesive layer containing a flame retardant described later, the adhesion between the base fabric and the adhesive layer, the adhesive strength, and the like become better.
  • the base material used for the synthetic leather may be a single-layer base material that is only a base fabric, or may be a base material that has a multilayer structure in which a sheet having physical properties according to the purpose and a base fabric are laminated. Good.
  • a skin layer is a well-known skin layer used for a synthetic leather, it can apply to the synthetic leather of this indication without a restriction
  • the skin layer can be formed by applying a composition for forming a skin layer containing a resin to the surface of the release agent layer of the temporary support having the release agent layer and drying it. .
  • polyurethane examples include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. When long-term durability is required, polycarbonate-based polyurethane is preferable. .
  • the polyurethane contained in the skin layer forming composition may be aqueous or solvent-based.
  • the polyurethane used in the composition for forming the skin layer one type may be used alone, or two or more types may be used. When two or more types of polyurethane are used, for example, a polycarbonate-based polyurethane which is a preferable polyurethane and a polyurethane other than the polycarbonate-based polyurethane may be used in combination.
  • water-based polyurethane a polyether-based polyurethane (homopolymer) or a polycarbonate-based polyurethane (homopolymer), or a mixture or copolymer of a polyether-based polyurethane and a polycarbonate-based polyurethane is used.
  • 0.01% to 10%, preferably 0.05% to 5%, more preferably 0.1% to 2% of carboxyl groups are introduced by mass ratio with respect to the polyurethane base.
  • water-based polyurethane water-based polyurethane.
  • the water-based polyurethane may have sufficient water dispersibility and dry film formability due to the presence of the carboxyl group. it can.
  • the solvent-based polyurethane include at least one solvent-based polyurethane selected from the group consisting of polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof, which can be dissolved in an organic solvent.
  • the solvent-based polyurethane may be a one-component system or a two-component system.
  • the skin layer preferably has a crosslinked structure.
  • a cross-linked structure is introduced into an aqueous polyurethane
  • a carboxyl group and a cross-linking agent are added by adding a cross-linking agent to the skin layer forming composition.
  • a crosslinking agent that can be used in the composition for forming the skin layer in order to form a crosslinked structure include conventionally known crosslinking agents.
  • Examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline-based crosslinking agent.
  • a carbodiimide crosslinking agent from the viewpoint of suppressing polyurethane hydrolysis.
  • a crosslinked structure is introduced into a solvent-based polyurethane
  • a solvent-based polyurethane is used as a main agent and a polydiisocyanate as a crosslinking component is used in combination.
  • a crosslinked structure can be formed during heat curing of the polyurethane.
  • the polyurethane used for forming the skin layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) in the range of 2 MPa to 40 MPa at 100% modulus. More preferably, the polyurethane is capable of forming a film in the range of 10 MPa.
  • the preferable hardness of the polyurethane used for the said skin layer in this specification shows the hardness after forming a crosslinked structure in a skin layer.
  • a commercially available product may be used as the polyurethane contained in the composition for forming the skin layer.
  • Examples of commercially available products that can be used for the composition for forming a skin layer include DIC Corporation, Crisbon (registered trademark) NY373 (trade name), and the like.
  • the skin layer may contain other components in addition to a resin such as polyurethane as a main ingredient and a solvent for dissolving the resin.
  • Other components that can be included in the skin layer include, for example, the aforementioned crosslinking agents, crosslinking accelerators, colorants, brightening agents (for example, pearl agents, metallic pigments, etc.), light-resistant stabilizers, ultraviolet absorbers, and antioxidants. Agents, touch improvers, film-forming aids, flame retardants, foaming agents and the like.
  • the colorant include colored organic resin particles in which a colorant is contained in organic resin fine particles selected from urethane resin particles, acrylic resin particles, silicone resin particles, and the like.
  • the average particle diameter of the organic resin fine particles used as the colorant is preferably in the range of 0.01 ⁇ m to 1.0 ⁇ m, and more preferably in the range of 0.05 ⁇ m to 0.8 ⁇ m.
  • the design property of synthetic leather improves because a skin layer contains a coloring agent.
  • the flame retardance of synthetic leather improves more by adding well-known flame retardants, such as a phosphorus type
  • the film thickness of the skin layer is not particularly limited and is appropriately selected according to the purpose.
  • the thickness of the skin layer after drying is preferably about 10 ⁇ m to 50 ⁇ m, more preferably about 10 ⁇ m to 30 ⁇ m.
  • the synthetic leather of the present disclosure has an adhesive layer containing a flame retardant (hereinafter sometimes simply referred to as an adhesive layer) on the surface of the skin layer on the base fabric side. That is, the skin layer is located on the surface opposite to the surface on the base fabric side of the adhesive layer.
  • the adhesive layer can be formed using an adhesive layer forming composition containing an adhesive and a flame retardant.
  • a polyurethane adhesive can be used to form the adhesive layer.
  • the polyurethane that can be used for forming the adhesive layer include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. When long-term durability is required, polycarbonate-based polyurethane is preferable.
  • the polyurethane used for the adhesive layer may be water-based or solvent-based, similar to the polyurethane used for the skin layer.
  • the polyurethane used for forming the adhesive layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) and having a 100% modulus in the range of 2 MPa to 20 MPa.
  • a polyurethane that can form a film in a range is more preferable.
  • the polyurethane used for the adhesive layer is preferably the same as the polyurethane used for the skin layer or a polyurethane capable of forming a more flexible film from the viewpoint of further improving the flexibility of the resulting synthetic leather.
  • the polyurethane contained in the composition for forming an adhesive layer may be a commercially available product.
  • Examples of commercially available products that can be used for the composition for forming an adhesive layer include DIC Corporation, Crisbon TA205FT, and the like.
  • the adhesive layer contains a flame retardant.
  • the flame retardancy of the synthetic leather of the present disclosure can be further improved. Therefore, the synthetic leather of the present disclosure is suitably used for interior materials for aircrafts and vehicles.
  • the flame retardant include metal hydroxide, phosphorus flame retardant, and nitrogen-phosphorus flame retardant.
  • a flame retardant is also available as a commercial item, for example, Arkroma Japan Co., Ltd. product, PEKOFLAM (registered trademark) STC powder, and the like.
  • the content of the flame retardant is preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of polyurethane as the main component of the adhesive layer.
  • an adhesive layer-forming composition containing polyurethane and a flame retardant is applied to the surface of the skin layer, and dried by heating to form an adhesive layer having a desired thickness.
  • a forming coating liquid layer is formed.
  • the base fabric described above and the adhesive layer forming composition layer are brought into thermal contact with each other, and the adhesive contained in the adhesive layer forming composition layer is reactively cured to form an adhesive layer, The adhesion between the adhesive layer and the base fabric can be performed simultaneously, and then the temporary support can be peeled off to obtain a synthetic leather.
  • a cross-linking agent and a cross-linking accelerator may be added to the adhesive layer for the purpose of improving curability.
  • a crosslinking agent and a crosslinking accelerator are selected according to the kind of polyurethane used for an adhesive layer. Examples of the crosslinking agent and crosslinking accelerator that can be used in the composition for forming an adhesive layer include the same ones as those described above for the composition for forming a skin layer.
  • the crosslinking agent may be used in combination with a crosslinking accelerator suitable for the crosslinking agent. What is necessary is just to select suitably content of the crosslinking agent in the composition for contact bonding layer considering the intensity
  • the thickness of the adhesive layer after drying is preferably about 20 ⁇ m to 100 ⁇ m, more preferably in the range of 30 ⁇ m to 80 ⁇ m. When the thickness of the adhesive layer is within the above range, a synthetic leather having sufficient elasticity and strength is formed.
  • the synthetic leather of the present disclosure may have other layers in addition to the base fabric, the adhesive layer, and the skin layer as long as the effects are not impaired.
  • Examples of other layers include an intermediate layer and a surface treatment layer.
  • the synthetic leather of the present disclosure has an intermediate between the above-described skin layer and the adhesive layer depending on purposes such as further improving the strength of the skin layer or improving the flexibility and cushioning properties of the synthetic leather. It may have a layer.
  • the intermediate layer There is no particular limitation on the structure of the intermediate layer. From the viewpoint of strength and flexibility, an intermediate layer containing polyurethane is preferred.
  • the polyurethane used for the intermediate layer may be water-based or solvent-based, similar to the polyurethane used for the skin layer.
  • the polyurethane used for forming the intermediate layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) and having a 100% modulus in the range of 2 MPa to 20 MPa. A polyurethane that can form a film in a range is more preferable.
  • the intermediate layer may be a resin layer containing bubbles, for example, a polyurethane resin intermediate layer containing bubbles for the purpose of improving cushioning properties.
  • polyurethane may be used as the polyurethane that can be used for forming the intermediate layer.
  • examples of commercially available polyurethane products that can be used for forming the intermediate layer include DIC Corporation, Crisbon TK1015T, and the like.
  • the thickness of the intermediate layer can be appropriately adjusted according to the purpose.
  • the thickness of the intermediate layer after drying is preferably 30 ⁇ m to 350 ⁇ m, more preferably 50 ⁇ m to 250 ⁇ m.
  • middle layer contains a flame retardant.
  • both the adhesive layer and the intermediate layer contain a flame retardant, the flame retardancy of the synthetic leather is further improved.
  • FIG. 1 is a schematic cross-sectional view showing an embodiment of the synthetic leather 10 of the present invention.
  • a synthetic leather (sometimes referred to as a first embodiment) 10 of the embodiment shown in FIG. 1 includes the base fabric 12 described above and a flame retardant provided on one surface of the base fabric 12.
  • the skin layer 16 is provided on the adhesive layer 14 and the surface of the adhesive layer 14 opposite to the surface in contact with the base fabric 12.
  • that the synthetic leather 10 includes the base cloth 12, the adhesive layer 14, and the skin layer 16 means that the adhesive layer 14 and the skin layer 16 exist in this order from the base fabric 12 side. The existence of other layers provided as desired is not denied.
  • a composition for forming a skin layer containing a resin, preferably polyurethane, is applied to the surface of the release agent layer of the temporary support having a release agent layer, for example, with a sealed or open coating head.
  • the skin layer forming composition layer can be formed, and the formed skin layer forming composition layer can be obtained by heating and drying.
  • the skin layer can be formed to a desired thickness by adjusting the formulation of the composition for forming the skin layer, the coating amount, and the like.
  • Examples of the temporary support used for forming the skin layer include a temporary support having a release agent layer on the surface and a desired embossed pattern (uneven pattern) formed on the surface on which the skin layer is formed. be able to.
  • a temporary support it is formed by using a temporary support having a concavo-convex pattern formed on the surface, and applying a composition for forming a skin layer on the surface of the temporary support on which the release agent layer is formed.
  • a leather-like uneven pattern formed in advance on the temporary support is transferred to the skin layer, and after peeling the temporary support, a skin layer having an uneven pattern in the direction is formed.
  • corrugated pattern to a skin layer is not limited above, For example, when thermocompression bonding the some layer containing a skin layer, an uneven
  • the polyurethane which can be used for the composition for forming the skin layer is as described above.
  • the thickness of the skin layer after drying is preferably about 10 ⁇ m to 50 ⁇ m, more preferably about 10 ⁇ m to 30 ⁇ m.
  • An adhesive layer is provided on the surface of the formed skin layer.
  • the adhesive layer is provided on the surface opposite to the surface on which the uneven pattern of the skin layer is formed.
  • the adhesive layer forming composition containing polyurethane and a flame retardant is applied to the surface of the skin layer with a sealed or open coating head to form the adhesive layer.
  • a composition layer is formed, and the formed adhesive layer forming composition layer is heated and dried to form an adhesive layer forming coating liquid layer having a desired thickness.
  • the adhesive contained in the composition layer for forming the adhesive layer is reaction-cured, and the adhesive layer is formed and the adhesive layer and the base fabric are adhered at the same time. By peeling, synthetic leather can be obtained.
  • the heating temperature and heating time for promoting the curing reaction are appropriately selected depending on the type of adhesive contained in the adhesive layer forming composition. .
  • the heating temperature is preferably in the range of 30 ° C. to 80 ° C.
  • the heating time is preferably in the range of 12 hours to 72 hours.
  • thermocompression bonding it is preferable to perform laminating by using a known apparatus such as a roll nip apparatus at a heating temperature in the range of 100 ° C. to 150 ° C.
  • the raised fiber of the base fabric infiltrates into the adhesive layer forming coating liquid layer by bringing the raised side into close contact with the adhesive layer forming coating liquid layer. With the adhesive layer cured, the adhesion between the base fabric and the adhesive layer is further improved.
  • a laminate of a skin layer and an adhesive layer forming composition layer is formed on a temporary support, and the adhesive layer and the base fabric are bonded.
  • the temporary support having a release layer is peeled off, and the elasticity, strength, and flame retardancy are good, and the smoke during combustion is Suppressed synthetic leather, for example, synthetic leather having a layer structure as shown in FIG. 1 can be obtained.
  • FIG. 2 is a schematic cross-sectional view showing a synthetic leather (sometimes referred to as a second embodiment) 20 according to another embodiment of the present invention.
  • a synthetic leather sometimes referred to as a second embodiment
  • an intermediate layer 18 is provided between the adhesive layer 14 and the skin layer 16.
  • the elasticity, flexibility, shape followability, etc. of the synthetic leather 20 become better by providing the intermediate layer 18 between the adhesive layer 14 and the skin layer 16 as desired. .
  • intermediate layer There is no particular limitation on the structure of the intermediate layer. From the viewpoint of strength and flexibility, an intermediate layer containing polyurethane is preferred.
  • the intermediate layer is preferably coated with an intermediate layer forming composition containing polyurethane on the surface of the skin layer opposite to the temporary support. Then, the intermediate layer forming composition layer is formed, and the formed intermediate layer forming composition layer is heated and dried to form a laminate having a skin layer and an intermediate layer on the temporary support. can do. By repeating the application of the composition for forming an intermediate layer and heating and drying twice or more, an intermediate layer having an arbitrary thickness can be formed.
  • the intermediate layer may be a polyurethane intermediate layer containing bubbles for the purpose of improving cushioning properties.
  • An example of a method for forming a polyurethane intermediate layer containing bubbles will be described.
  • a composition for forming a creamy intermediate layer containing bubbles is prepared by adjusting the viscosity of a composition for forming an intermediate layer containing polyurethane as appropriate using a solvent and a thickener, and stirring and mechanically foaming the composition.
  • the obtained creamy intermediate layer forming composition is applied onto the above-described skin layer to form an intermediate layer forming composition layer that encloses bubbles, and this is dried and cured to enclose bubbles.
  • a polyurethane interlayer can be formed.
  • the intermediate layer forming composition that performs mechanical foaming may contain a foaming agent, a foam stabilizer, a crosslinking agent, a thickener, and the like.
  • the intermediate layer forming composition can be mechanically stirred while entraining air, and the intermediate layer forming composition is mechanically foamed into a cream.
  • a method of obtaining a composition for forming an intermediate layer which is mechanically foamed in a cream form by continuously stirring while feeding a predetermined amount of air using an oak mixer, a pin mixer or the like can be used.
  • a known coating device such as a normal knife coater, comma coater, roll coater, lip coater, etc. Can do.
  • the intermediate layer forming composition may include a thermally expanded microcapsule, 4,4 ′′ -oxybiz (benzenesulfonyl hydrazide), azodicarbonamide, sodium hydrogen carbonate, and the like.
  • examples thereof include a method in which a chemical foaming agent is contained, applied onto the above-described skin layer, and then heated and dried to foam the chemical foaming agent to form an intermediate layer containing bubbles.
  • An adhesive layer forming composition layer is formed by applying an adhesive layer forming composition to the surface of the formed intermediate layer opposite to the skin layer in the same manner as in the first embodiment.
  • the layer structure shown in FIG. 2 is obtained by closely adhering the surface having the formed adhesive layer forming composition layer and the base fabric, curing the adhesive layer forming composition layer, and then peeling the temporary support.
  • a synthetic leather having the following can be obtained.
  • the composition for forming an intermediate layer may contain a foaming agent, a foam stabilizer, a crosslinking agent, a thickener, and the like in addition to the chemical foaming agent.
  • components such as a film forming aid, a pigment, a flame retardant, a filler, an antiaging agent, an ultraviolet absorber, and an aromatic can be further added to the intermediate layer forming composition.
  • the synthetic leather of the present disclosure may be further provided with other layers as long as the effect is not impaired in addition to the above-described skin layer, adhesive layer, and optionally provided intermediate layer provided on at least one surface of the base fabric. Good.
  • the formation of a surface treatment layer that is an example of other layers will be described below.
  • the surface treatment layer can be formed by applying a surface treatment agent composition containing an aqueous emulsion resin or an organic solvent surface treatment agent composition to the surface of the skin layer described above.
  • a surface treatment agent composition containing an aqueous emulsion resin or an organic solvent surface treatment agent composition
  • the resin used for forming the surface treatment layer for example, polyurethane, acrylic, elastomer and the like are preferable, and polyurethane is more preferable.
  • the surface treatment layer can contain a crosslinking agent, an organic filler, a lubricant, a flame retardant, and the like. For example, when the surface treatment layer contains an organic filler, a lubricant, etc., a smooth feel is imparted to the skin material, and the wear resistance is further improved.
  • the synthetic leather of the present disclosure has good durability and flame retardancy, and includes a base fabric in which smoke generation during combustion is suppressed and an adhesive layer containing a flame retardant, and thus has good durability and flame retardancy. .
  • it can be suitably used in various fields such as automobile interior materials, railway vehicle interior parts, aircraft interior parts, furniture, shoes, footwear, bags, building interior and exterior members, clothing cover materials, clothing linings, Even in the case where the surface of a member having a complicated three-dimensional shape such as a seat or a chair is covered, the same feel and appearance as when natural leather is used can be achieved.
  • Example 1 Polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33) which is a flame retardant fiber, rayon fiber (LOI value: 19) which is a cellulosic fiber, and phenolic carbon fiber (LOI value: 33) which is a carbon fiber. ) Using a 22-th blended yarn obtained by spinning using three types of fibers, a knitted fabric having a knitting structure of mokurodi, a thickness of 0.9 mm, and a weight of 310 g / m 2 (knitted fabric) A base fabric was obtained. The blend ratio of the polyvinylidene chloride fiber, the rayon fiber, and the phenolic carbon fiber was 35:35:30 in terms of mass ratio.
  • the LOI value measured by JIS K7201 (2006) of the obtained base fabric was 37.
  • a temporary support a cleaved release paper (Dai Nippon Printing Co., Ltd., DE-41: paper thickness average 140 ⁇ m) having a surface release treatment and having a release layer was used.
  • the composition for forming a skin layer was sufficiently mixed to obtain a composition for forming a skin layer.
  • the composition for forming the skin layer is about 30 ⁇ m after drying using an open type coating head coating apparatus.
  • the coating film was dried with hot air using a hot air dryer at 100 ° C. for 2 minutes to form a skin layer on the temporary support.
  • the obtained skin layer was observed visually, it was a uniform skin layer without a pinhole.
  • Hard yellowing-type polycarbonate polyurethane adhesive with 100% modulus of 2.5 MPa made by DIC Corporation, Crisbon TA205FT: trade name
  • 100 parts by mass / non-decabro halogen-based flame retardant (antimony combined type) 20 parts by mass manufactured by Maruhishi Oil Chemical Co., Ltd., Nonnen (registered trademark) SAN-2: trade name
  • Solvent mixed solvent with a mass ratio of DMF and methyl ethyl ketone (MEK) of 85:15
  • MEK methyl ethyl ketone
  • the components of the adhesive layer forming composition were sufficiently mixed to obtain an adhesive layer forming composition.
  • the adhesive layer forming composition was applied using an open-type coating head in an amount such that the thickness after drying was 50 ⁇ m, at 100 ° C. It dried for 2 minutes, the coating liquid layer for contact bonding layer formation was formed, and the laminated body for synthetic leather formation was obtained.
  • the obtained layered product for forming synthetic leather was brought into contact with the coating liquid layer for forming the adhesive layer and the base fabric, laminated with a nip device, wound up, and maintained at 50 ° C. for 48 hours.
  • the curing reaction of the adhesive contained in the forming coating liquid layer was advanced to form an adhesive layer in close contact with the base fabric.
  • the temporary support was peeled off to obtain the synthetic leather of Example 1 having an adhesive layer and a skin layer in this order on the surface of the base fabric.
  • Example 2 In the same manner as in Example 1, a skin layer was temporarily formed on the release paper. Next, components of the following formulation were sufficiently mixed to prepare an intermediate layer forming composition.
  • Composition for intermediate layer formation ⁇ Hard yellowing polycarbonate urethane resin with 100% modulus of 5 MPa (DIC Corporation, Crisbon TK1015T) 100 parts by weight -Thermal expansion beads 4 parts by mass (Nippon Ferrite Co., Ltd., Expandel 920DU120) -4.6 part by weight of an amine chain extender (BASF Japan, Lalomin (registered trademark) C260) ⁇ Colored organic resin fine particles 5 parts by mass (DIC Corporation, Dirac Color Series) ⁇ Phosphorus flame retardant (Acroma Japan Co., Ltd., PEKOFLAM (registered trademark) ATC powder) 30 parts by mass / solvent (mass ratio of DMF, 1-methoxy-2-propanol (PGM) and ethyl acetate: mixed solvent of 24:38:
  • the obtained intermediate layer-forming composition is subjected to a film thickness after drying using an open coating coating apparatus.
  • the coating was applied in an amount of 200 ⁇ m, and the coating film was dried with hot air using a hot air dryer at 170 ° C. for 2 minutes to expand the thermally expanded beads, thereby forming an intermediate layer containing bubbles on the skin layer.
  • a coating liquid layer for forming an adhesive layer was formed on the surface of the formed intermediate layer opposite to the skin layer in the same manner as in Example 1 to obtain a laminate for forming synthetic leather.
  • the obtained layered product for forming synthetic leather is brought into contact with the coating layer for forming the adhesive layer and the same base fabric as used in Example 1, and after drying the coating layer for forming the adhesive layer Then, it was adhered to the base fabric by thermocompression bonding.
  • the synthetic leather of Example 2 provided with the intermediate layer containing the bubbles in the synthetic leather of Example 1 was obtained.
  • the obtained synthetic leather of Example 2 was excellent in appearance, and the elasticity and feel when pressed with a finger were even better than those of Example 1.
  • Comparative Example 1 In place of the base fabric used in Example 1, two types of fibers, a flame retardant polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33) and a cellulosic rayon fiber (LOI value: 19), were used. A base fabric was obtained by knitting the same as the base fabric in Example 1, using a 22nd blended yarn obtained by spinning fibers at a mass ratio of 65:35. A synthetic leather of Comparative Example 1 was produced in the same manner as in Example 1 except that was used.
  • LOI value: 33 flame retardant polyvinylidene chloride-acrylic copolymer fiber
  • LOI value cellulosic rayon fiber
  • Comparative Example 2 In place of the base fabric used in Example 1, 22th yarn consisting only of a polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33), which is a flame retardant fiber, was used. A synthetic leather of Comparative Example 2 was produced in the same manner as in Example 1 except that a base fabric was obtained by the same knitting and the obtained base fabric was used.
  • LOI value: 33 polyvinylidene chloride-acrylic copolymer fiber
  • Combustion length The length of combustion spread from the ignition location was measured. According to the standard, 20 cm or less is accepted. A: Combustion length within 15 cm B: Combustion length exceeds 15 cm, within 20 cm C: Combustion length exceeds 20 cm (failure level)
  • Falling object burning time The time for which falling object combustion from the ignited point was continued was measured. According to the standard, a sample that stops combustion within 5 seconds is accepted. A: Falling object does not burn, combustion stops immediately B: Combustion time of falling object within 5 seconds C: Combustion time of falling object exceeds 5 seconds (failed level)
  • Smoke test The smoke test of synthetic leather was measured using a smoke chamber according to the BSS 7238 flaming method (measurement of smoke specific optical density of aircraft interior materials Boeing standard) and evaluated according to the following criteria. When the smoke generation concentration is 100 or less, it is evaluated that the smoke generation property can be practically used. (Evaluation criteria) A: Smoke density is 80 or less B: Smoke density exceeds 80, 100 or less C: Smoke density exceeds 100
  • the synthetic leathers of Examples 1 and 2 are excellent in all of flame retardancy, fire spread prevention and scratch resistance, smoke generation during combustion is suppressed, and visibility during combustion is expected to be ensured. I understand that I can do it. For this reason, it turns out that it can be used conveniently for the sheet
  • the synthetic leather of Comparative Example 1 using flame retardant fibers and cellulosic fibers as the base fabric is slightly inferior to the Examples in terms of suppressing smoke generation during combustion, and Comparative Example 2 using only flame retardant fibers was carried out. Compared with Example 1, the fire spread prevention property was low, and the smoke generation property was at a level causing a practical problem.

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  • Textile Engineering (AREA)
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Abstract

A synthetic leather having: a base cloth which is knitted from a yarn that includes a flame retardant fiber having a limiting oxygen index of 25 or greater, a cellulosic fiber, and a carbon fiber, the base cloth having a limiting oxygen index of 25 or greater; an adhesive layer including a flame retardant agent and provided on at least one surface of the base cloth; and an outermost layer provided on the surface of the adhesive layer that is opposite to the surface in contact with the base cloth.

Description

合成皮革Synthetic leather
　本開示は、合成皮革に関する。 This disclosure relates to synthetic leather.
　近年、自動車内装部品（例えば、インストルメントパネル、ドアトリム、座席、天井など）、鉄道車両、航空機内装部品（例えば、トリム、座席、天井など）、家具、靴等の履物、鞄、建装用内外装部材、衣類表装材、衣類裏地、壁装材などには、天然皮革や繊維性シートに代えて、耐久性に優れる合成皮革が多用されている。例えば、航空機用内装部品や自動車内装品に用いる合成皮革は、軽量で耐久性があること、耐火性が良好であることが必要である。既述の基礎的な特性に加え、ある程度の厚み及び適度の弾力性を有し、天然の皮革に近い感触をもつ合成皮革が求められている。
　合成皮革は、寸法安定性、加工性が良好であるという観点から、一般的には、基布などの繊維質シート表面に、適度の弾力性を調整するための柔軟な樹脂層と、皮革様の外観を有し、耐摩耗性に優れた表皮層を有する。 In recent years, automobile interior parts (for example, instrument panels, door trims, seats, ceilings, etc.), railway vehicles, aircraft interior parts (for example, trims, seats, ceilings, etc.), furniture, footwear such as shoes, bags, interior and exterior for construction Synthetic leather having excellent durability is often used in place of natural leather and fibrous sheets for members, clothing covering materials, clothing lining materials, wall covering materials, and the like. For example, synthetic leather used for aircraft interior parts and automobile interior parts needs to be lightweight and durable and have good fire resistance. In addition to the basic characteristics described above, there is a need for a synthetic leather that has a certain thickness and moderate elasticity, and has a feel close to that of natural leather.
Synthetic leather generally has a flexible resin layer for adjusting moderate elasticity on the surface of a fibrous sheet such as a base fabric, and leather-like, from the viewpoint of good dimensional stability and processability. And has a skin layer excellent in wear resistance.
　気密性の高い航空機、車両、自動車等の内装品については、内装品に使用される合成皮革には、良好な耐火性が望まれている。合成皮革の耐火性としては、火炎に接触しても燃え難いこと、火炎に接触して一部が燃えても燃え広がり難いこと、及び燃えた場合に発煙し難いこと等が重要とされている。
　気密性が高い航空機、車両、自動車などの内部では、火災による発煙が著しい場合、視界が遮られたり、煙を吸い込んだりする可能性が高まる。このため、特に、航空機用内装部品、車両内装部品、自動車内装品等に使用される合成皮革では、耐火性として、燃え難さに加えて、火炎に触れた場合の発煙が抑制されることが望まれている。火炎に触れた場合でも、発煙が抑制され、発煙濃度が低いことは、気密性が高い空間内での視界確保の観点から重要な基準となる。 For interior parts such as highly airtight aircrafts, vehicles, automobiles, etc., good fire resistance is desired for synthetic leather used for interior parts. As fire resistance of synthetic leather, it is important that it is difficult to burn even if it comes into contact with flame, that it is difficult to spread even if part of it burns in contact with flame, and that it is difficult to emit smoke when burned.
Inside a highly airtight aircraft, vehicle, automobile, etc., if the smoke from the fire is significant, there is a high possibility that the field of view will be blocked or smoke will be inhaled. For this reason, in particular, in synthetic leather used for aircraft interior parts, vehicle interior parts, automobile interior parts, etc., in addition to flame resistance, smoke generation when touching a flame is suppressed as fire resistance. It is desired. Even when a flame is touched, smoke generation is suppressed and the smoke concentration is low, which is an important criterion from the viewpoint of ensuring visibility in a highly airtight space.
　難燃性向上を目的として、基布に窒素系、リン酸系の難燃剤を含浸させてなる合成皮革が提案されている（特開２００６－７７３４９号公報参照）。 For the purpose of improving flame retardancy, synthetic leather in which a base fabric is impregnated with a nitrogen-based or phosphoric acid-based flame retardant has been proposed (see Japanese Patent Application Laid-Open No. 2006-77349).
　さらに、本願出願人は、先に、限界酸素指数（ＬＯＩ値）が２５以上の難燃繊維とセルロース系繊維とを含む糸を用いた両面編組織を有し、質量が１５０ｇ／ｍ２～２５０ｇ／ｍ２の編製体であり、該編製体のＬＯＩ値が２５以上である合成皮革用基布上に、水系ポリウレタン接着層、及び水系ポリウレタン表皮層をこの順で有する合成皮革を提案した（特開２０１３－０７２１４１号公報参照）。 Further, the applicant of the present application has a double-sided knitted structure using a yarn containing a flame retardant fiber having a limiting oxygen index (LOI value) of 25 or more and a cellulosic fiber, and has a mass of 150 g / m 2 to 250 g. / m a knitting member 2, the LOI value of knitting made body on the base fabric for artificial leather is 25 or more, water-based polyurethane adhesive layer, and has proposed a synthetic leather having a water-based polyurethane skin layer in this order (Japanese (See JP 2013-0721141).
　しかしながら、特開２００６－７７３４９号公報に記載の合成皮革は、基布に用いられる織布や不織布の厚みや強度が充分ではない場合、例えば、座席シートなどに使用した場合に仕上り性が劣るという問題がある。さらに、製造時には、基布に難燃剤などを含浸させ、その後、乾燥させ、樹脂層と接着させるため、製造工程が煩雑であり、使用する難燃剤によっては、燃焼時の有毒ガス又は発煙の要因ともなり得るという問題があった。
　また、特開２０１３－０７２１４１号公報に記載の合成皮革は、天然の皮革に近い感触をもち、耐久性、加工性、及び難燃性が良好であり、燃焼しても有毒ガスの発生が抑制されるという機能を有してはいるが、燃焼時の発煙の抑制という観点ではなお改良の余地がある。 However, the synthetic leather described in Japanese Patent Application Laid-Open No. 2006-77349 is inferior in finish when the thickness and strength of the woven fabric and nonwoven fabric used for the base fabric are not sufficient, for example, when used for a seat seat or the like. There's a problem. Furthermore, at the time of manufacture, the base fabric is impregnated with a flame retardant, etc., and then dried and adhered to the resin layer. Therefore, the manufacturing process is complicated, and depending on the flame retardant used, toxic gas or fuming factor at the time of combustion There was a problem that it could be both.
In addition, the synthetic leather described in JP2013-0721141 has a feeling close to that of natural leather, has good durability, processability, and flame retardancy, and suppresses generation of toxic gas even when burned. However, there is still room for improvement in terms of suppressing smoke generation during combustion.
　本発明の一実施形態の課題は、難燃性が良好であり、燃焼時の発煙が抑制された合成皮革を提供することにある。 An object of one embodiment of the present invention is to provide a synthetic leather that has good flame retardancy and has reduced smoke generation during combustion.
　上記課題を解決する手段は、以下の実施形態を含む。
［１］　限界酸素指数（以下、ＬＯＩ値と称することがある）が２５以上の難燃繊維と、セルロース系繊維と、炭素繊維とを含む糸の編製体であり、かつ、限界酸素指数が２５以上である基布と、前記基布の少なくとも一方の面上に備えられる難燃剤を含む接着層と、前記接着層の、前記基布側の面とは反対の面に備えられる表皮層と、を有する合成皮革である。 Means for solving the above problems includes the following embodiments.
[1] A knitted product of a yarn including a flame retardant fiber having a critical oxygen index (hereinafter sometimes referred to as LOI value) of 25 or more, a cellulosic fiber, and a carbon fiber, and a critical oxygen index of 25 The base fabric, the adhesive layer containing a flame retardant provided on at least one surface of the base fabric, the skin layer provided on the surface of the adhesive layer opposite to the surface on the base fabric side, Is a synthetic leather having
［２］　前記難燃繊維が、アラミド繊維、メタ系アラミド繊維、ポリフェニレンサルファイド繊維、アクリル繊維、塩化ビニル繊維、ポリクラール繊維、塩化ビニリデン繊維、アクリル－塩化ビニル共重合体繊維、及びアクリル－塩化ビニリデン共重合体繊維から選ばれた１種以上を含む［１］に記載の合成皮革である。 [2] The flame retardant fiber is aramid fiber, meta-aramid fiber, polyphenylene sulfide fiber, acrylic fiber, vinyl chloride fiber, polyclar fiber, vinylidene chloride fiber, acrylic-vinyl chloride copolymer fiber, and acrylic-vinylidene chloride. The synthetic leather according to [1], including at least one selected from polymer fibers.
［３］　前記炭素繊維が、ポリアクリロニトリル（ＰＡＮ）系繊維、ピッチ系繊維、及びフェノール系繊維から選ばれた１種以上を含む［１］又は［２］に記載の合成皮革である。
［４］　編製体を構成する糸の全質量に対する前記炭素繊維の含有量が２０質量％～４０質量％であり、前記編製体を構成する糸の全質量に対する前記セルロース系繊維の含有量が２５質量％～４５質量％であり、かつ、前記難燃繊維と前記炭素繊維の総含有量が、前記セルロース系繊維の含有量よりも多い［１］～［３］のいずれか１つに記載の合成皮革。
［５］　前記接着層と、前記表皮層との間に、さらに、中間層を備える［１］～［４］のいずれか１つに記載の合成皮革。
［６］　前記中間層が、難燃剤を含有する［５］に記載の合成皮革。 [3] The synthetic leather according to [1] or [2], wherein the carbon fiber includes one or more selected from polyacrylonitrile (PAN) fiber, pitch fiber, and phenol fiber.
[4] The carbon fiber content is 20% by mass to 40% by mass with respect to the total mass of the yarn constituting the knitted body, and the cellulosic fiber content is 25 with respect to the total mass of the yarn constituting the knitted body. The total content of the flame retardant fiber and the carbon fiber is greater than the content of the cellulosic fiber by 1% to 45% by mass, and is any one of [1] to [3] Synthetic leather.
[5] The synthetic leather according to any one of [1] to [4], further comprising an intermediate layer between the adhesive layer and the skin layer.
[6] The synthetic leather according to [5], wherein the intermediate layer contains a flame retardant.
　本発明の一実施形態によれば、難燃性が良好であり、燃焼時の発煙が抑制された合成皮革を提供することができる。 According to one embodiment of the present invention, it is possible to provide a synthetic leather that has good flame retardancy and has reduced smoke generation during combustion.
本開示における合成皮革の一態様を示す概略断面図である。It is a schematic sectional drawing showing one mode of synthetic leather in this indication. 本開示における合成皮革の別の態様を示す概略断面図である。It is a schematic sectional drawing which shows another aspect of the synthetic leather in this indication.
　以下、本開示の合成皮革について、具体的な実施形態の例を挙げて詳細に説明するが、本発明は、以下の実施形態に何ら限定されるものではなく、本発明の目的の範囲内において、適宜変更を加えて実施することができる。 Hereinafter, the synthetic leather of the present disclosure will be described in detail with examples of specific embodiments. However, the present invention is not limited to the following embodiments, and is within the scope of the object of the present invention. It can be implemented with appropriate modifications.
　本明細書において「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を意味する。
　本明細書において、組成物中の各成分の量は、各成分に該当する物質が組成物中に複数存在する場合には、特に断らない限り、組成物中に存在する複数の物質の合計量を意味する。
　本明細書において、「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。
　各図面において同一の符号を用いて示される構成要素は、同一の構成要素であることを意味する。 In the present specification, a numerical range indicated by using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means.
In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.
Constituent elements indicated using the same reference numerals in the drawings mean the same constituent elements.
　本明細書中に段階的に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、ある数値範囲で記載された上限値又は下限値は、実施例に示されている値に置き換えてもよい。 In the numerical ranges described stepwise in the present specification, the upper limit value or lower limit value described in a numerical range may be replaced with the upper limit value or lower limit value of the numerical range described in other steps. . Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.
＜合成皮革＞
　本開示の合成皮革は、ＬＯＩ値が２５以上の難燃繊維と、セルロース系繊維と、炭素繊維とを含む糸の編製体であり、ＬＯＩ値が２５以上である基布と、前記基布の少なくとも一方の面上に備えられる難燃剤を含む接着層と、前記接着層の、前記基布側の面とは反対の面に備えられる表皮層と、を有する。
　なお、合成皮革の基布とは、合成皮革の各層を形成する基材であって、編製体、織物、不織布などから選ばれる布である基材を指す。本開示における基布は編製体、即ち、繊維を編んで形成された編物である。 <Synthetic leather>
The synthetic leather of the present disclosure is a knitted body of yarn containing a flame retardant fiber having a LOI value of 25 or more, a cellulosic fiber, and a carbon fiber, and a base fabric having a LOI value of 25 or more, An adhesive layer including a flame retardant provided on at least one surface; and a skin layer provided on a surface of the adhesive layer opposite to the surface on the base fabric side.
The synthetic leather base fabric refers to a base material that forms each layer of the synthetic leather and is a fabric selected from a knitted fabric, a woven fabric, a non-woven fabric, and the like. The base fabric in the present disclosure is a knitted body, that is, a knitted fabric formed by knitting fibers.
〔基布〕
　本開示の合成皮革に用いられる基布は、ＬＯＩ値が２５以上の難燃繊維（以下、「難燃繊維」と称することがある）と、セルロース系繊維と、炭素繊維と、を含む糸の編製体であり、かつ、編製体である基布自体のＬＯＩ値が２５以上である。
　基布に用いられる編製体は、少なくとも既述の３種の異なる繊維を含む糸を用いて編製される。
　限界酸素指数（ＬＯＩ値）とは、ものが燃え続けるのに必要な酸素濃度を示し、ＪＩＳ　Ｋ７２０１（２００６年）（ＡＳＴＭ　Ｄ２８６３）に記載の方法で測定される。通常、空気中の酸素濃度が２１．２％程度であるため、ＬＯＩ値が２５以上であれば、難燃性が良好であるといえる。 [Base fabric]
The base fabric used for the synthetic leather of the present disclosure is a yarn including a flame retardant fiber having a LOI value of 25 or more (hereinafter sometimes referred to as “flame retardant fiber”), a cellulosic fiber, and a carbon fiber. The LOI value of the base fabric itself, which is a knitted body and is a knitted body, is 25 or more.
The knitted body used for the base fabric is knitted using yarns containing at least the three kinds of different fibers described above.
The limiting oxygen index (LOI value) indicates the oxygen concentration necessary for an object to continue to burn, and is measured by the method described in JIS K7201 (2006) (ASTM D2863). Usually, since the oxygen concentration in the air is about 21.2%, if the LOI value is 25 or more, it can be said that the flame retardancy is good.
　基布が車両用内装材などに使用される合成皮革用の基布であることを考慮すれば、編製のし易さ、得られる基布の柔軟性及び耐久性が良好であるという観点から、編製体の編製に使用される糸は１６番手～４０番手程度の太さであることが好ましい。なお、本明細書における「番手」とは「綿番手(cotton　yarn　count」）を意味し、糸１ポンド（１Lb：０．４５２５９２３７ｋｇ）の重さで８４０ヤード（１yard：７６８．０９６ｍ）の長さであることを表す。１ポンドの重さの糸が１６８０ヤードの長さとなるものを２番手という。従って、番手の数値が小さいほど、太い繊維であることを示す。
　なお、ＳＩ単位系の１ｔｅｘは、１０００ｍ長さの糸が１ｇの質量を有することを表し、下記換算式を用いることにより綿番手からｔｅｘに変換することができる。
　　　　(換算式)　　　　１ｔｅｘ＝５９０．５４番手（綿番手） Considering that the base fabric is a base fabric for synthetic leather used for vehicle interior materials, etc., from the viewpoint of ease of knitting, flexibility and durability of the resulting base fabric, It is preferable that the yarn used for knitting the knitted body has a thickness of about 16 to 40. In this specification, “count” means “cotton count”, and the weight is 1 pound (1 Lb: 0.452525937 kg) and the length is 840 yards (1yard: 768.096 m). It represents that. A thread that weighs 1 pound and is 1680 yards long is called second. Therefore, it shows that it is a thick fiber, so that a numerical value of a count is small.
In addition, 1 tex of the SI unit system represents that a 1000-m-long yarn has a mass of 1 g, and can be converted from cotton count to tex by using the following conversion formula.
(Conversion formula) 1 tex = 590.54 (cotton count)
（難燃繊維）
　基布に使用される難燃繊維は、ＬＯＩ値が２５以上であれば特に制限はない。なお、難燃繊維とは不燃繊維ではなく、例えば、繊維又は繊維の編製体に炎が接触したとき、焦げたり、炎の接触部分が燃焼したりした場合でも、燃え広がらず、炎が離れた場合には速やかに燃焼が止む繊維を指す。
　難燃繊維としては、柔軟でボリューム感のある編製体を形成し得るという観点からは、難燃性の合成繊維が好ましい。基布に用い得る難燃繊維としては、具体的には、メタ系アラミド繊維を含むアラミド繊維、ポリフェニレンサルファイド繊維、ポリクラール繊維、塩化ビニリデン繊維、アクリル－塩化ビニル共重合体繊維、アクリル－塩化ビニリデン共重合体繊維、ポリベンゾイミダゾール繊維、塩化ビニリデン繊維、及び塩化ビニル系繊維が挙げられる。また、難燃繊維ではない繊維に対して難燃加工してＬＯＩ値を２５以上とした繊維を、基布における難燃繊維として用いることができる。難燃加工してＬＯＩ値を２５以上とした繊維としては、難燃化ポリノジック繊維、難燃化ポリエステル繊維、難燃化アクリル系繊維、及び難燃化レーヨン繊維などが挙げられる。
　なお、製造の容易性、及び発煙抑制の観点からは、繊維を構成する材料自体が難燃性である難燃繊維を用いることが好ましい。 (Flame retardant fiber)
The flame retardant fiber used for the base fabric is not particularly limited as long as the LOI value is 25 or more. Incombustible fiber is not non-combustible fiber. For example, when a flame comes into contact with a fiber or a knitted fabric of fiber, even if the burned part burns or the contact part of the flame burns, the flame does not spread and the flame leaves. In some cases, it refers to a fiber that stops burning quickly.
As the flame retardant fiber, a flame retardant synthetic fiber is preferable from the viewpoint that a knitted body having a flexible and volume feeling can be formed. Specific examples of flame retardant fibers that can be used for the base fabric include aramid fibers including meta-aramid fibers, polyphenylene sulfide fibers, polyclar fibers, vinylidene chloride fibers, acrylic-vinyl chloride copolymer fibers, and acrylic-vinylidene chloride copolymers. Examples include polymer fibers, polybenzimidazole fibers, vinylidene chloride fibers, and vinyl chloride fibers. Moreover, the fiber which carried out the flame-retardant process with respect to the fiber which is not a flame-retardant fiber, and made LOI value 25 or more can be used as a flame-retardant fiber in a base fabric. Examples of the fiber having a LOI value of 25 or more by flame retardant processing include flame retardant polynosic fiber, flame retardant polyester fiber, flame retardant acrylic fiber, and flame retardant rayon fiber.
From the viewpoint of ease of production and suppression of smoke generation, it is preferable to use a flame retardant fiber in which the material itself constituting the fiber is flame retardant.
　難燃性、基布に編製したときの強度及び風合いに優れるという観点から、既述の難燃繊維のなかでも、アラミド繊維、メタ系アラミド繊維、ポリフェニレンサルファイド繊維、アクリル繊維、塩化ビニル繊維、ポリクラール繊維、塩化ビニリデン繊維、アクリル－塩化ビニル共重合体繊維、及びアクリル－塩化ビニリデン共重合体繊維から選ばれた１種以上を含むことが好ましい。 Among the flame retardant fibers described above, aramid fiber, meta-aramid fiber, polyphenylene sulfide fiber, acrylic fiber, vinyl chloride fiber, polyclar from the viewpoint of excellent flame retardancy, strength and texture when knitted on a base fabric It is preferable to include one or more selected from fibers, vinylidene chloride fibers, acrylic-vinyl chloride copolymer fibers, and acrylic-vinylidene chloride copolymer fibers.
　本開示における難燃繊維は、ＬＯＩ値が２５以上である。難燃繊維のＬＯＩ値は、好ましくは２６以上であり、より好ましくは２８以上である。
　車両用内装材などに使用される合成皮革用の基布であることを考慮すれば、編製体の編製に使用する難燃繊維を含む糸の太さは、１６番手～４０番手程度の太さであることが好ましい。 The flame retardant fiber in the present disclosure has a LOI value of 25 or more. The LOI value of the flame retardant fiber is preferably 26 or more, more preferably 28 or more.
Considering that it is a base fabric for synthetic leather used for vehicle interior materials, the thickness of the yarn containing flame retardant fibers used for knitting a knitted body is about 16th to 40th. It is preferable that
（セルロース系繊維）
　基布に用いられるセルロース系繊維には特に制限はなく、公知のセルロース系繊維を任意に選択して使用することができる。セルロース系繊維としては、綿、麻、キュプラ、及びレーヨンなどが挙げられる。
　なかでも、得られる基布の柔軟性の観点からは、綿、及びレーヨンから選ばれる１種以上が好ましい。
　綿、レーヨン等のセルロース系繊維は、単独でのＬＯＩ値は１７～１９程度であり、易燃性繊維といえる。しかし、既述の難燃繊維及び後述の炭素繊維と組み合わせて編製体とすることで、セルロース系繊維の特性を生かしつつ、編製体としての基布全体のＬＯＩ値が２５以上となる態様で使用される。
　基布の編製に用いる糸にセルロース系繊維を含むことで、燃焼時にセルロース系繊維が炭化して、編製体の燃焼速度を遅延させることができる。 (Cellulose fiber)
There is no restriction | limiting in particular in the cellulose fiber used for a base fabric, A well-known cellulose fiber can be selected arbitrarily and can be used. Examples of cellulosic fibers include cotton, hemp, cupra, and rayon.
Especially, from a viewpoint of the softness | flexibility of the base fabric obtained, 1 or more types chosen from cotton and rayon are preferable.
Cellulose fibers such as cotton and rayon have a LOI value of about 17 to 19 alone, and can be said to be flammable fibers. However, it is used in a mode in which the LOI value of the entire base fabric as the knitted body is 25 or more while taking advantage of the characteristics of the cellulosic fiber by combining the flame retardant fiber described above and the carbon fiber described later into a knitted body. Is done.
By including the cellulosic fiber in the yarn used for knitting the base fabric, the cellulosic fiber is carbonized at the time of combustion, and the burning rate of the knitted body can be delayed.
（炭素繊維）
　炭素繊維は、有機繊維等の炭素繊維の前駆体を加熱炭化処理して得られ、繊維の全質量に対し、質量比で９０質量％以上が炭素で構成される繊維を指す。
　本開示の合成皮革の基布の製造に用いられる炭素繊維には特に制限はない。
　なかでも、炭素繊維は、アクリル繊維を用いたＰＡＮ（ポリアクリロニトリル）系炭素繊維、ピッチを原料とするピッチ系炭素繊維、フェノール樹脂を用いたフェノール系炭素繊維から選ばれる少なくとも１種を含むことが好ましい。即ち、基布は、炭素繊維として、ポリアクリロニトリル（ＰＡＮ）系繊維、ピッチ系繊維、及びフェノール系繊維から選ばれた１種以上を含んで紡糸された糸を用いて編製されることが好ましい。
　炭素繊維は、炭素以外の元素として、主として原料の樹脂由来の水素、酸素を含有する。しかし、炭素繊維は、リンなどの元素は含まないため、燃焼し難く、燃焼しても発煙が極めて少ない。さらに、炭素繊維は、熱伝導性が高いため、基布が炭素繊維を含むことにより、着火時の延焼を効果的に抑制できる。 (Carbon fiber)
Carbon fiber is obtained by heating and carbonizing a precursor of carbon fiber such as organic fiber, and refers to a fiber in which 90% by mass or more is composed of carbon with respect to the total mass of the fiber.
There is no particular limitation on the carbon fiber used for the production of the synthetic leather base fabric of the present disclosure.
Especially, carbon fiber contains at least 1 sort (s) chosen from the PAN (polyacrylonitrile) type | system | group carbon fiber using an acrylic fiber, the pitch type | system | group carbon fiber which uses a pitch as a raw material, and the phenol type | system | group carbon fiber using a phenol resin. preferable. That is, it is preferable that the base fabric is knitted using, as carbon fibers, a yarn spun containing at least one selected from polyacrylonitrile (PAN) fibers, pitch fibers, and phenol fibers.
Carbon fiber mainly contains hydrogen and oxygen derived from the raw material resin as elements other than carbon. However, since carbon fiber does not contain elements such as phosphorus, it is difficult to burn, and even when burned, it produces very little smoke. Furthermore, since carbon fiber has high thermal conductivity, it is possible to effectively suppress the spread of fire at the time of ignition when the base fabric includes carbon fiber.
　基布の編製に用いられる、少なくとも、既述の難燃繊維、セルロース系繊維、及び炭素繊維を含む糸において、各繊維の含まれる態様には特に制限はない。例えば、難燃繊維を含む糸と、セルロース系繊維を含む糸と、炭素繊維を含む糸の３種の糸とを用いて編製してもよく、３種の繊維のうち２種を含む混紡糸と、残りの１種を含む糸とを用いて編製してもよく、既述の３種の繊維を含む混紡糸を用いて編製してもよい。 There is no particular limitation on the mode in which each fiber is contained in the yarn containing at least the above-mentioned flame retardant fiber, cellulosic fiber, and carbon fiber used for knitting the base fabric. For example, it may be knitted using three types of yarns including a flame retardant fiber, a cellulose fiber, and a carbon fiber, and a mixed yarn including two of the three types of fibers. And the yarn containing the remaining one type may be knitted, or may be knitted using the blended yarn containing the three types of fibers described above.
　基布の難燃性を低下させることなく、既述のセルロース繊維の炭化による燃焼速度の優れた遅延効果を得るためには、セルロース系繊維は、既述の難燃繊維及び炭素繊維と混紡して用いることが好ましい。
　即ち、燃焼速度の遅延効果、発煙抑制効果の観点からは、編製体を作製するのに用いられる糸は、難燃性繊維とセルロース系繊維との混紡糸、炭素繊維とセルロース系繊維との混紡糸、及び難燃性繊維とセルロース系繊維と炭素繊維との混紡糸から選ばれる混紡糸であることが好ましく、なかでも、難燃性繊維とセルロース系繊維と炭素繊維との混紡糸であることが、難燃性、発煙の抑制効果がより良好となるという観点から好ましい。
　既述の３種の繊維を含む糸を用いることにより、得られる編製体のＬＯＩ値を２５以上とすることができる。
　基布における難燃繊維、セルロース系繊維、及び炭素繊維の含有率は、得られる編製体のＬＯＩ値を２５以上とし得る範囲で適宜調整される。 In order to obtain the excellent retarding effect of the burning rate due to carbonization of the cellulose fiber described above without reducing the flame retardancy of the base fabric, the cellulosic fiber is blended with the flame retardant fiber and carbon fiber described above. Are preferably used.
That is, from the viewpoint of the effect of retarding the burning rate and the effect of suppressing smoke generation, the yarn used for producing the knitted product is a blended yarn of flame retardant fiber and cellulosic fiber, or a blend of carbon fiber and cellulosic fiber. It is preferably a blended yarn selected from yarns and blended yarns of flame retardant fibers, cellulosic fibers, and carbon fibers, and in particular, blended yarns of flame retardant fibers, cellulosic fibers, and carbon fibers. However, it is preferable from a viewpoint that a flame retardance and the suppression effect of smoke generation become more favorable.
By using the yarn containing the three types of fibers described above, the LOI value of the obtained knitted body can be 25 or more.
The flame retardant fiber, cellulosic fiber, and carbon fiber content in the base fabric is appropriately adjusted within a range where the LOI value of the resulting knitted fabric can be 25 or more.
　本開示の合成皮革に用いられる基布は、難燃繊維と、セルロース系繊維と、炭素繊維とを含む糸により編製された編製体であり、かつ、編製体自体のＬＯＩ値もまた２５以上である。
　前記編製体を構成する糸の全質量に対する前記炭素繊維の含有量が２０質量％～４０質量％であり、前記編製体を構成する糸の全質量に対する前記セルロース系繊維の含有量が２５質量％～４５質量％であり、かつ、前記難燃繊維と前記炭素繊維の総含有量が、前記セルロース系繊維の含有量よりも多いことが好ましい。
　即ち、得られる基布の難燃性がより良好となるという観点から、編製体における難燃繊維と炭素繊維との総含有量は、５０質量％を超えることが好ましく、編製体を構成する糸の全質量に対する難燃繊維と炭素繊維との合計量の割合が６０質量％以上９０質量％以下であることがより好ましい。
　また、編製体を構成する糸の全質量に対する炭素繊維の含有量は、発煙抑制効果の観点から２０質量％～４０質量％であることが好ましく、３０質量％～４０質量％であることがより好ましい。
　また、得られる基布の柔軟性、風合いがより良好であるという観点から、編製体を構成する糸の全質量に対するセルロース系繊維の含有量は２５質量％～４５質量％であることが好ましく、２５質量％～４０質量％であることがより好ましい。 The base fabric used for the synthetic leather of the present disclosure is a knitted body knitted with a yarn containing flame retardant fibers, cellulosic fibers, and carbon fibers, and the LOI value of the knitted body itself is 25 or more. is there.
The carbon fiber content is 20% by mass to 40% by mass with respect to the total mass of the yarn constituting the knitted body, and the cellulosic fiber content is 25% by mass with respect to the total mass of the yarn constituting the knitted body. It is preferable that the total content of the flame retardant fiber and the carbon fiber is larger than the content of the cellulosic fiber.
That is, from the viewpoint that the flame resistance of the obtained base fabric becomes better, the total content of flame retardant fibers and carbon fibers in the knitted fabric is preferably more than 50% by mass, and the yarn constituting the knitted fabric It is more preferable that the ratio of the total amount of the flame retardant fiber and the carbon fiber with respect to the total mass is 60 mass% or more and 90 mass% or less.
Further, the content of the carbon fiber with respect to the total mass of the yarn constituting the knitted body is preferably 20% by mass to 40% by mass and more preferably 30% by mass to 40% by mass from the viewpoint of the smoke generation suppressing effect. preferable.
In addition, from the viewpoint that the flexibility and texture of the obtained base fabric are better, the content of the cellulosic fibers with respect to the total mass of the yarn constituting the knitted body is preferably 25% by mass to 45% by mass, More preferably, the content is 25% by mass to 40% by mass.
　編製体は、好ましくは両面編の組織を有する。
　基布としての編製体を、両面編の組織とすることで、基布に起因する合成皮革の風合い、及び弾力性がより良好になる。
　難燃繊維とセルロース系繊維と炭素繊維とを含む糸により両面編組織を有する編製体を編製する場合に使用される糸としては、得られる基布の弾力性、強度の観点から、太さ２０番手～４０番手程度、糸密度は、ウェール：２０本／インチ（＝２５．４ｍｍ）～５０本／インチ、コース：１５本／インチ～７０本／インチ程度であることが好ましい。
　このようにして得られた編製体は、質量が１５０ｇ／ｍ２～４００ｇ／ｍ２の範囲であることが好ましく、１７５ｇ／ｍ２～３５０ｇ／ｍ２の範囲であることがより好ましい。 The knitted body preferably has a double-sided knitted structure.
By making the knitted body as the base fabric into a double-sided knitted structure, the texture and elasticity of the synthetic leather resulting from the base fabric become better.
As a yarn used when knitting a knitted body having a double-sided knitted structure with a yarn containing a flame retardant fiber, a cellulosic fiber, and a carbon fiber, from the viewpoint of the elasticity and strength of the resulting base fabric, a thickness of 20 The yarn density is preferably about 20 yarns / inch (= 25.4 mm) to 50 yarns / inch and the course: 15 yarns / inch to 70 yarns / inch.
The thus obtained knitted body is preferably mass is in the range of 150g / m 2 ~ 400g / m 2, and more preferably in the range of 175g / m 2 ~ 350g / m 2.
　編製体の組織には特に制限はなく、難燃繊維とセルロース系繊維と炭素繊維とを撚り合わせた混紡糸で、均一な編製体としてもよく、難燃繊維からなる糸とセルロース系繊維からなる糸と炭素繊維からなる糸とを別々に使用した両面編組織であり、片面に主として難燃繊維及び炭素系繊維が、他方の面に主としてセルロース繊維が露出するように組織される編製体であってもよい。
　難燃繊維からなる糸とセルロース系繊維からなる糸と炭素繊維からなる糸とを用いて両面編組織を編製する場合には、例えば、より難燃性が求められる側に、難燃繊維からなる糸及び炭素繊維からなる糸を露出するように編製することで特定面の難燃性の向上を図ることができる。 The structure of the knitted body is not particularly limited, and it is a mixed spun yarn obtained by twisting flame retardant fibers, cellulosic fibers and carbon fibers, and may be a uniform knitted body. It consists of yarns made of flame retardant fibers and cellulosic fibers. It is a double-sided knitted structure that uses yarn and carbon fiber yarn separately, and is a knitted body that is structured so that mainly flame-retardant fibers and carbon-based fibers are exposed on one side, and cellulose fibers are mainly exposed on the other side. May be.
When knitting a double-sided knitted structure using yarns made of flame retardant fibers, yarns made of cellulosic fibers and yarns made of carbon fibers, for example, made of flame retardant fibers on the side where more flame retardancy is required By knitting the yarn and the yarn made of carbon fiber so as to be exposed, the flame retardance of the specific surface can be improved.
　なかでも、編製体の風合い、具体的には柔軟性がより優れるという観点からは、基布の編製に好適な糸は、撚り糸（混紡糸）であり、上記難燃性効果向上の観点からも、難燃繊維とセルロース系繊維と炭素繊維とを含む混紡糸が好ましい。
　即ち、難燃繊維、セルロース系繊維、及び炭素系繊維を含む混紡糸を用いた両面編組織とする場合には、セルロース系繊維に起因する良好な風合いが得られ、燃焼時には、燃焼し難い難燃性に加え、混紡糸中のセルロース系繊維が燃焼時に炭化することで編製体の燃焼速度を遅延させ、かつ、熱伝導性が高く、燃焼時の発煙が抑制された炭素繊維が存在することで、基布の難燃性、及び燃焼時の発煙抑制効果が顕著となる。 Among them, from the viewpoint that the texture of the knitted body, specifically, the flexibility is more excellent, the yarn suitable for knitting the base fabric is a twisted yarn (mixed yarn), and also from the viewpoint of improving the flame retardancy effect. A blended yarn containing flame retardant fiber, cellulosic fiber and carbon fiber is preferred.
That is, when a double-sided knitted structure using a blended yarn containing flame retardant fibers, cellulosic fibers, and carbon fibers, a good texture resulting from the cellulosic fibers can be obtained, and it is difficult to burn during combustion. In addition to the flammability, there must be carbon fibers that retard the burning speed of the knitted body by carbonizing the cellulose fibers in the blended yarn during combustion, and have high thermal conductivity and suppressed smoke generation during combustion. Thus, the flame retardancy of the base fabric and the smoke suppression effect during combustion become significant.
　両面編組織の好ましい態様としては、緻密な両面編みであるモクロディ編み、両面編の変化組織の一つであり、両面編みと袋編みとを交互に繰り返す組織であるポンチローマ（ｐｏｎｔｅｒｏｍｅ）編等が、強度と弾力性が良好で、得られた合成皮革の加工性に優れる観点から好ましい。
　例えば、モクロディ編み組織を有する編製体の場合には、両面編みであってハイゲージであるため、緻密であり、織物に似た外観を呈し、厚み感があって、かつ、編製体特有の柔軟性と伸縮性とを兼ね備える。基布をモクロディ編みの編製体とする場合には、既述の難燃繊維とセルロース系繊維と炭素繊維との混紡糸を用いることが好ましい。なお、ゲージとは単位長さ当たりの網目の数を示し、ハイゲージとは、単位長さ当たりの網目の数が多い、密度の高い編製体を指す。 Preferable embodiments of the double-sided knitting structure include a mocrodi knitting that is a dense double-sided knitting, a changeable structure of double-sided knitting, and a pontoroma knitting that is a structure in which double-sided knitting and bag knitting are alternately repeated. From the viewpoint of good strength and elasticity and excellent workability of the obtained synthetic leather.
For example, in the case of a knitted body having a mocrodi knitted structure, since it is double-sided knitting and high gauge, it is dense, has an appearance similar to a woven fabric, has a feeling of thickness, and has flexibility unique to the knitted body Combines elasticity. When the base fabric is a knitted body of mocrodi knitting, it is preferable to use the above-mentioned blended yarn of flame retardant fiber, cellulosic fiber and carbon fiber. The gauge indicates the number of meshes per unit length, and the high gauge indicates a high-density knitted body having a large number of meshes per unit length.
　また、例えば、ポンチローマ編み組織を有する編製体では、片面に主として第１の糸が露出し、他方の面に主として第２の糸が露出する編製体を形成し得るため、例えば、片面に難燃繊維及び炭素系繊維からなる糸を露出させて、それを表面側に使用し、易燃性のセルロース系繊維が露出する面を裏面とすることで、セルロース系繊維か主として露出する面が難燃繊維及び炭素系繊維からなる層により保護された編製体とすることができる。 Further, for example, in a knitted body having a punched Roman knitting structure, a knitted body in which the first yarn is mainly exposed on one side and the second yarn is mainly exposed on the other surface can be formed. It is difficult to expose the surface of mainly cellulose fibers, by exposing the yarn made of fuel fiber and carbon fiber and using it on the surface side, and making the surface where the flammable cellulosic fiber is exposed as the back surface. It can be set as the knitted body protected by the layer which consists of a fuel fiber and a carbon-type fiber.
　基布の編製に両面編みを採用する場合には、同一の組成の混紡糸を用いてもよく、互いに混紡率の異なる２種の混紡糸を用いてもよい。いずれの場合にも、前記３種類の繊維を併用することにより、基布全体の難燃性が改良され、燃焼時の発煙が効果的に抑制される。 When double-sided knitting is adopted for knitting the base fabric, blended yarns having the same composition may be used, or two types of blended yarns having different blending rates may be used. In any case, the combined use of the three kinds of fibers improves the flame retardancy of the entire base fabric and effectively suppresses smoke generation during combustion.
　基布として、難燃繊維と、天然繊維であり通気性と風合いに優れたセルロース系繊維と、高強度、難燃性であり、熱伝導度が高く、加熱しても発煙し難い炭素繊維と、を含む糸の編製体を用いているために、強度と風合いに優れ、難燃性が良好であり、発煙が抑制された、ＬＯＩ値が高い基布となる。本開示の合成皮革は、更に、後述するように接着層が難燃剤を含むために、基布の難燃性と接着層の難燃性が相俟って、難燃性が良好な合成皮革となるものと考えている。 As a base fabric, a flame retardant fiber, a cellulosic fiber that is a natural fiber and excellent in breathability and texture, and a carbon fiber that is high in strength and flame retardant, has high thermal conductivity, and does not emit smoke even when heated. Thus, a base fabric having a high LOI value, excellent in strength and texture, excellent in flame retardancy, suppressed smoke generation, is used. The synthetic leather according to the present disclosure further includes a synthetic leather having good flame retardancy due to a combination of the flame retardance of the base fabric and the flame retardance of the adhesive layer because the adhesive layer contains a flame retardant as described later. I think that will be.
　本開示の合成皮革は、基布の難燃性が良好であり、燃焼時の発煙が抑制されることに加え、強度と弾力性に優れ、柔軟であることから、この基布を用いて形成された合成皮革は強度と加工性に優れる。
　なお、編製体である基布は、少なくとも片面に起毛を有していてもよい。起毛は常法により形成することができる。基布の起毛を有する面と、後述する難燃剤を含む接着層とを接触させることで、基布と、接着層との密着性、密着強度等がより良好となる。
　合成皮革に用いられる基材は、基布のみである単層の基材であってもよく、目的に応じた物性を有するシートと基布とを積層した重層構造を有する基材であってもよい。 The synthetic leather of the present disclosure is formed using this base fabric because the flame resistance of the base fabric is good, smoke generation during combustion is suppressed, and it is excellent in strength and elasticity, and is flexible. The synthetic leather is excellent in strength and processability.
In addition, the base fabric which is a knitted body may have raising at least on one side. Brushed can be formed by a conventional method. By bringing the surface of the base fabric having the raised portions into contact with an adhesive layer containing a flame retardant described later, the adhesion between the base fabric and the adhesive layer, the adhesive strength, and the like become better.
The base material used for the synthetic leather may be a single-layer base material that is only a base fabric, or may be a base material that has a multilayer structure in which a sheet having physical properties according to the purpose and a base fabric are laminated. Good.
　以下、本開示の合成皮革が有する各層について説明する。 Hereinafter, each layer of the synthetic leather of the present disclosure will be described.
〔表皮層〕
　表皮層は、合成皮革に用いられる公知の表皮層であれば、本開示の合成皮革に制限なく適用することができる。
　なかでも、耐傷性、加工性に優れるという点から、表皮層はポリウレタンを含むことが好ましい。
　以下に詳述するように、表皮層は、離型剤層を有する仮支持体の離型剤層表面に、樹脂を含む表皮層形成用組成物を塗布し、乾燥して形成することができる。 (Skin layer)
If a skin layer is a well-known skin layer used for a synthetic leather, it can apply to the synthetic leather of this indication without a restriction | limiting.
Especially, it is preferable that a skin layer contains a polyurethane from the point that it is excellent in scratch resistance and workability.
As will be described in detail below, the skin layer can be formed by applying a composition for forming a skin layer containing a resin to the surface of the release agent layer of the temporary support having the release agent layer and drying it. .
　表皮層形成用組成物に使用できるポリウレタンとしては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物等が挙げられ、長期耐久性が必要な場合、ポリカーボネート系ポリウレタンが好適である。
　表皮層形成用組成物に含まれるポリウレタンは、水系であっても、溶剤系であってもよい。
　表皮層形成用組成物に使用されるポリウレタンは、１種を単独で用いてもよく、２種以上を用いてもよい。ポリウレタンを２種以上用いる場合、例えば、好ましいポリウレタンであるポリカーボネート系ポリウレタンと、ポリカーボネート系ポリウレタン以外のポリウレタンとを併用してもよい。 Examples of the polyurethane that can be used in the composition for forming the skin layer include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. When long-term durability is required, polycarbonate-based polyurethane is preferable. .
The polyurethane contained in the skin layer forming composition may be aqueous or solvent-based.
As the polyurethane used in the composition for forming the skin layer, one type may be used alone, or two or more types may be used. When two or more types of polyurethane are used, for example, a polycarbonate-based polyurethane which is a preferable polyurethane and a polyurethane other than the polycarbonate-based polyurethane may be used in combination.
　前記水系ポリウレタンとしては、ポリエーテル系ポリウレタン（単独重合体）又はポリカーボネート系ポリウレタン（単独重合体）、若しくはポリエーテル系ポリウレタンとポリカーボネート系ポリウレタンとの混合物又は共重合体を用い、既述のポリウレタン主剤の分子鎖の一部に、ポリウレタン主剤に対して、質量比で０．０１％～１０％、好ましくは０．０５％～５％、より好ましくは０．１％～２％のカルボキシル基が導入された水系ポリウレタンが挙げられる。既述の質量比の範囲で、ポリウレタン主剤に対してカルボキシル基が導入された場合、カルボキシル基の存在に起因して、水系ポリウレタンは、充分な水分散性と乾燥成膜性とを有することができる。
　溶剤系ポリウレタンとしては、有機溶剤に溶解可能な、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物からなる群より選択される少なくとも１種の溶剤系ポリウレタンが挙げられる。溶剤系ポリウレタンは１液系であっても、２液系であってもよい。 As the water-based polyurethane, a polyether-based polyurethane (homopolymer) or a polycarbonate-based polyurethane (homopolymer), or a mixture or copolymer of a polyether-based polyurethane and a polycarbonate-based polyurethane is used. In part of the molecular chain, 0.01% to 10%, preferably 0.05% to 5%, more preferably 0.1% to 2% of carboxyl groups are introduced by mass ratio with respect to the polyurethane base. And water-based polyurethane. When a carboxyl group is introduced into the polyurethane main component within the mass ratio range described above, the water-based polyurethane may have sufficient water dispersibility and dry film formability due to the presence of the carboxyl group. it can.
Examples of the solvent-based polyurethane include at least one solvent-based polyurethane selected from the group consisting of polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof, which can be dissolved in an organic solvent. The solvent-based polyurethane may be a one-component system or a two-component system.
　また、表皮層の膜強度がより良好となるという観点からは、表皮層は架橋構造を有することが好ましい。
　水系ポリウレタンに架橋構造を導入する態様を例に挙げれば、例えば、ポリウレタン主剤にカルボキシル基が導入されたものを用いる場合、表皮層形成用組成物に架橋剤を加えることで、カルボキシル基と架橋剤とが反応して架橋構造を形成することができる。
　架橋構造を形成するために表皮層形成用組成物に用い得る架橋剤としては、従来公知の架橋剤を挙げることができる。例えば、イソシアネート架橋剤、エポキシ架橋剤、アジリジン架橋剤、カルボジイミド架橋剤、オキサゾリン系架橋剤等が挙げられる。なかでも、カルボジイミド架橋剤を用いることが、ポリウレタンの加水分解を抑制する観点から好ましい。 Further, from the viewpoint that the film strength of the skin layer becomes better, the skin layer preferably has a crosslinked structure.
For example, in the case where a cross-linked structure is introduced into an aqueous polyurethane, for example, when using a polyurethane main component having a carboxyl group introduced, a carboxyl group and a cross-linking agent are added by adding a cross-linking agent to the skin layer forming composition. Can react with each other to form a crosslinked structure.
Examples of the crosslinking agent that can be used in the composition for forming the skin layer in order to form a crosslinked structure include conventionally known crosslinking agents. Examples thereof include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a carbodiimide crosslinking agent, and an oxazoline-based crosslinking agent. Among these, it is preferable to use a carbodiimide crosslinking agent from the viewpoint of suppressing polyurethane hydrolysis.
　また、溶剤系ポリウレタンに架橋構造を導入する態様を例に挙げれば、例えば、溶剤系ポリウレタンを主剤として用い、架橋成分としてのポリジイソシアネートと併用する態様が挙げられる。ポリジイソシアネートを併用することで、ポリウレタンの加熱硬化時に架橋構造を形成することができる。 Further, if an embodiment in which a crosslinked structure is introduced into a solvent-based polyurethane is taken as an example, for example, an embodiment in which a solvent-based polyurethane is used as a main agent and a polydiisocyanate as a crosslinking component is used in combination. By using polydiisocyanate in combination, a crosslinked structure can be formed during heat curing of the polyurethane.
　表皮層の形成に使用するポリウレタンは、ＪＩＳ　Ｋ６７７２（１９９４年）で測定した硬さが、１００％モジュラスで２ＭＰａ～４０ＭＰａの範囲にあるフィルムを形成し得るポリウレタンであることが好適であり、３ＭＰａ～１０ＭＰａの範囲にあるフィルムを形成し得るポリウレタンであることがより好ましい。
　なお、本明細書における上記表皮層に用いるポリウレタンの好ましい硬さは、表皮層において、架橋構造を形成した後の硬さを示す。 The polyurethane used for forming the skin layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) in the range of 2 MPa to 40 MPa at 100% modulus. More preferably, the polyurethane is capable of forming a film in the range of 10 MPa.
In addition, the preferable hardness of the polyurethane used for the said skin layer in this specification shows the hardness after forming a crosslinked structure in a skin layer.
　表皮層形成用組成物に含まれるポリウレタンは市販品を用いてもよい。表皮層形成用組成物に用い得る市販品としては、例えば、ＤＩＣ（株）、クリスボン（登録商標）ＮＹ３７３（商品名）などが挙げられる。 A commercially available product may be used as the polyurethane contained in the composition for forming the skin layer. Examples of commercially available products that can be used for the composition for forming a skin layer include DIC Corporation, Crisbon (registered trademark) NY373 (trade name), and the like.
　表皮層は、主剤となるポリウレタン等の樹脂及び樹脂を溶解する溶剤に加え、さらに他の成分を含んでもよい。
　表皮層に含まれ得る他の成分としては、例えば、既述の架橋剤、架橋促進剤、着色剤、光輝剤（例えば、パール剤、メタリック顔料等）、耐光安定剤、紫外線吸収剤、酸化防止剤、感触向上剤、成膜助剤、難燃剤、発泡剤等が挙げられる。
　着色剤としては、例えば、ウレタン系樹脂粒子、アクリル系樹脂粒子、シリコーン系樹脂粒子などから選ばれる有機樹脂微粒子に着色剤が含まれてなる着色有機樹脂粒子などが挙げられ、なかでも、分散媒となるポリウレタン系樹脂に対する親和性、及び均一分散性の観点から、ポリカーボネート系の着色樹脂粒子を含有することが好ましい。
　着色剤として用いる有機樹脂微粒子の平均粒径は、一般的には、０．０１μｍ～１．０μｍの範囲であることが好ましく、より好ましくは、０．０５μｍ～０．８μｍの範囲である。
　例えば、表皮層が着色剤を含有することで、合成皮革の意匠性が向上する。
　また、表皮層が、リン系、ハロゲン系、無機金属系等の公知の難燃剤を添加することで合成皮革の難燃性がより向上する。 The skin layer may contain other components in addition to a resin such as polyurethane as a main ingredient and a solvent for dissolving the resin.
Other components that can be included in the skin layer include, for example, the aforementioned crosslinking agents, crosslinking accelerators, colorants, brightening agents (for example, pearl agents, metallic pigments, etc.), light-resistant stabilizers, ultraviolet absorbers, and antioxidants. Agents, touch improvers, film-forming aids, flame retardants, foaming agents and the like.
Examples of the colorant include colored organic resin particles in which a colorant is contained in organic resin fine particles selected from urethane resin particles, acrylic resin particles, silicone resin particles, and the like. From the viewpoint of the affinity for the polyurethane resin and the uniform dispersibility, it is preferable to contain polycarbonate colored resin particles.
In general, the average particle diameter of the organic resin fine particles used as the colorant is preferably in the range of 0.01 μm to 1.0 μm, and more preferably in the range of 0.05 μm to 0.8 μm.
For example, the design property of synthetic leather improves because a skin layer contains a coloring agent.
Moreover, the flame retardance of synthetic leather improves more by adding well-known flame retardants, such as a phosphorus type | system | group, a halogen type | system | group, an inorganic metal type | system | group, to a skin layer.
　表皮層の膜厚には特に制限はなく、目的に応じて適宜選択される。一般的には、強度及び外観の観点から、表皮層の乾燥後の膜厚は、１０μｍ～５０μｍ程度が好ましく、１０μｍ～３０μｍ程度がより好ましい。 The film thickness of the skin layer is not particularly limited and is appropriately selected according to the purpose. In general, from the viewpoint of strength and appearance, the thickness of the skin layer after drying is preferably about 10 μm to 50 μm, more preferably about 10 μm to 30 μm.
〔難燃剤を含む接着層〕
　本開示の合成皮革は、前記表皮層の基布側の面上に難燃剤を含む接着層（以下、単に接着層と称することがある）を有する。即ち、表皮層は、接着層の基布側の面とは反対側の面に位置する。
　接着層は、後述するように、接着剤と難燃剤とを含む接着層形成用組成物を用いて形成することができる。 [Adhesive layer containing flame retardant]
The synthetic leather of the present disclosure has an adhesive layer containing a flame retardant (hereinafter sometimes simply referred to as an adhesive layer) on the surface of the skin layer on the base fabric side. That is, the skin layer is located on the surface opposite to the surface on the base fabric side of the adhesive layer.
As will be described later, the adhesive layer can be formed using an adhesive layer forming composition containing an adhesive and a flame retardant.
　接着層の形成にはポリウレタン接着剤を使用することができる。接着層の形成に用い得るポリウレタンとしては、ポリカーボネート系ポリウレタン、ポリエーテル系ポリウレタン、ポリエステル系ポリウレタン及びこれらの変性物が挙げられ、長期耐久性が必要な場合ポリカーボネート系ポリウレタンが好適である。
　接着層に用いられるポリウレタンも、前記表皮層に用いられるポリウレタンと同様、水系であっても、溶剤系であってもよい。
　接着層の形成に使用するポリウレタンは、ＪＩＳ　Ｋ６７７２（１９９４年）で測定した硬さが、１００％モジュラスで２ＭＰａ～２０ＭＰａの範囲であるフィルムを形成し得るポリウレタンであることが好ましく、２ＭＰａ～８ＭＰａの範囲であるフィルムを形成し得るポリウレタンであることがより好ましい。
　接着層に用いるポリウレタンは、得られる合成皮革の柔軟性をより向上する観点から、表皮層に用いるポリウレタンと同等であるか、より柔軟な膜を形成し得るポリウレタンが好ましい。 A polyurethane adhesive can be used to form the adhesive layer. Examples of the polyurethane that can be used for forming the adhesive layer include polycarbonate-based polyurethane, polyether-based polyurethane, polyester-based polyurethane, and modified products thereof. When long-term durability is required, polycarbonate-based polyurethane is preferable.
The polyurethane used for the adhesive layer may be water-based or solvent-based, similar to the polyurethane used for the skin layer.
The polyurethane used for forming the adhesive layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) and having a 100% modulus in the range of 2 MPa to 20 MPa. A polyurethane that can form a film in a range is more preferable.
The polyurethane used for the adhesive layer is preferably the same as the polyurethane used for the skin layer or a polyurethane capable of forming a more flexible film from the viewpoint of further improving the flexibility of the resulting synthetic leather.
　接着層形成用組成物に含まれるポリウレタンは市販品を用いてもよい。接着層形成用組成物に用い得る市販品としては、例えば、ＤＩＣ（株）製、クリスボンＴＡ２０５ＦＴなどが挙げられる。 The polyurethane contained in the composition for forming an adhesive layer may be a commercially available product. Examples of commercially available products that can be used for the composition for forming an adhesive layer include DIC Corporation, Crisbon TA205FT, and the like.
（難燃剤）
　接着層は難燃剤を含有する。接着層が難燃剤を含有することで、本開示の合成皮革の難燃性をより向上させることができる。従って、本開示の合成皮革は航空機や車輌用等の内装材などに好適に用いられる。
　接着層に使用し得る難燃剤には特に制限はなく、公知のものを適宜使用することができる。難燃剤としては、例えば、金属水酸化物、リン系難燃剤、及び、窒素－リン系難燃剤などが挙げられる。
　難燃剤は市販品としても入手可能であり、例えば、アークロマジャパン（株）製、ＰＥＫＯＦＬＡＭ（登録商標）　ＳＴＣパウダーなどが挙げられる。
　難燃剤の含有量は、接着層の主剤となるポリウレタン１００質量部に対して、５質量部～４０質量部の範囲であることが好ましい。 (Flame retardants)
The adhesive layer contains a flame retardant. When the adhesive layer contains a flame retardant, the flame retardancy of the synthetic leather of the present disclosure can be further improved. Therefore, the synthetic leather of the present disclosure is suitably used for interior materials for aircrafts and vehicles.
There is no restriction | limiting in particular in the flame retardant which can be used for a contact bonding layer, A well-known thing can be used suitably. Examples of the flame retardant include metal hydroxide, phosphorus flame retardant, and nitrogen-phosphorus flame retardant.
A flame retardant is also available as a commercial item, for example, Arkroma Japan Co., Ltd. product, PEKOFLAM (registered trademark) STC powder, and the like.
The content of the flame retardant is preferably in the range of 5 to 40 parts by mass with respect to 100 parts by mass of polyurethane as the main component of the adhesive layer.
　後述するように、仮支持体上に、表皮層を形成した後、表皮層の表面にポリウレタンと難燃剤とを含む接着層形成用組成物を塗布し、加熱乾燥して所望の厚みの接着層形成用塗布液層を形成する。
　その後、既述の基布と、接着層形成用組成物層と、が接するようにして熱圧着させ、接着層形成用組成物層に含まれる接着剤を反応硬化させて接着層の形成と、接着層と基布との密着とを同時に行い、その後、仮支持体を剥離して、合成皮革を得ることができる。 As will be described later, after forming a skin layer on a temporary support, an adhesive layer-forming composition containing polyurethane and a flame retardant is applied to the surface of the skin layer, and dried by heating to form an adhesive layer having a desired thickness. A forming coating liquid layer is formed.
Thereafter, the base fabric described above and the adhesive layer forming composition layer are brought into thermal contact with each other, and the adhesive contained in the adhesive layer forming composition layer is reactively cured to form an adhesive layer, The adhesion between the adhesive layer and the base fabric can be performed simultaneously, and then the temporary support can be peeled off to obtain a synthetic leather.
　接着層には、硬化性向上を目的として、架橋剤、及び架橋促進剤を添加してもよい。
　架橋剤及び架橋促進剤は、接着層に用いられるポリウレタンの種類に応じて選択される。接着層形成用組成物に用い得る架橋剤及び架橋促進剤は、既述の表皮層形成用組成物において説明したものと同様のものが挙げられる。
　架橋剤は、架橋剤に適する架橋促進剤と併用してもよい。
　接着層形成用組成物における架橋剤の含有量は、接着層に求められる強度、柔軟性などを考慮して適宜選択すればよい。 A cross-linking agent and a cross-linking accelerator may be added to the adhesive layer for the purpose of improving curability.
A crosslinking agent and a crosslinking accelerator are selected according to the kind of polyurethane used for an adhesive layer. Examples of the crosslinking agent and crosslinking accelerator that can be used in the composition for forming an adhesive layer include the same ones as those described above for the composition for forming a skin layer.
The crosslinking agent may be used in combination with a crosslinking accelerator suitable for the crosslinking agent.
What is necessary is just to select suitably content of the crosslinking agent in the composition for contact bonding layer considering the intensity | strength, a softness | flexibility, etc. which are calculated | required by the contact bonding layer.
　接着層の乾燥後の厚みは、２０μｍ～１００μｍ程度であることが好ましく、より好ましくは３０μｍ～８０μｍの範囲である。接着層の厚みが上記範囲において、充分な弾力性と強度を有する合成皮革が形成される。 The thickness of the adhesive layer after drying is preferably about 20 μm to 100 μm, more preferably in the range of 30 μm to 80 μm. When the thickness of the adhesive layer is within the above range, a synthetic leather having sufficient elasticity and strength is formed.
　本開示の合成皮革は、前記基布、接着層及び表皮層に加えて、効果を損なわない限り、他の層を有していてもよい。他の層としては、例えば、中間層、表面処理層等が挙げられる。 The synthetic leather of the present disclosure may have other layers in addition to the base fabric, the adhesive layer, and the skin layer as long as the effects are not impaired. Examples of other layers include an intermediate layer and a surface treatment layer.
〔中間層〕
　本開示の合成皮革は、表皮層の強度をさらに向上させたり、合成皮革の柔軟性、クッション性を向上させたりするなどの目的に応じて、既述の表皮層と接着層との間に中間層を有していてもよい。 [Middle layer]
The synthetic leather of the present disclosure has an intermediate between the above-described skin layer and the adhesive layer depending on purposes such as further improving the strength of the skin layer or improving the flexibility and cushioning properties of the synthetic leather. It may have a layer.
　中間層の構成には特に制限はない。強度と柔軟性の観点からはポリウレタンを含有する中間層が好ましい。
　中間層に用いられるポリウレタンも、前記表皮層に用いられるポリウレタンと同様、水系であっても、溶剤系であってもよい。
　中間層の形成に使用するポリウレタンは、ＪＩＳ　Ｋ６７７２（１９９４年）で測定した硬さが、１００％モジュラスで２ＭＰａ～２０ＭＰａの範囲であるフィルムを形成し得るポリウレタンであることが好ましく、３ＭＰａ～１０ＭＰａの範囲であるフィルムを形成し得るポリウレタンであることがより好ましい。 There is no particular limitation on the structure of the intermediate layer. From the viewpoint of strength and flexibility, an intermediate layer containing polyurethane is preferred.
The polyurethane used for the intermediate layer may be water-based or solvent-based, similar to the polyurethane used for the skin layer.
The polyurethane used for forming the intermediate layer is preferably a polyurethane capable of forming a film having a hardness measured in accordance with JIS K6772 (1994) and having a 100% modulus in the range of 2 MPa to 20 MPa. A polyurethane that can form a film in a range is more preferable.
　中間層はクッション性向上などの目的で、気泡を内包する樹脂層、例えば、気泡を内包するポリウレタン樹脂中間層であってもよい。 The intermediate layer may be a resin layer containing bubbles, for example, a polyurethane resin intermediate layer containing bubbles for the purpose of improving cushioning properties.
　中間層の形成に用い得るポリウレタンは市販品を用いてもよい。中間層の形成に用い得るポリウレタンの市販品としては、例えば、ＤＩＣ（株）製、クリスボンＴＫ１０１５Ｔなどが挙げられる。 Commercially available polyurethane may be used as the polyurethane that can be used for forming the intermediate layer. Examples of commercially available polyurethane products that can be used for forming the intermediate layer include DIC Corporation, Crisbon TK1015T, and the like.
　中間層の厚みは、目的に応じて適宜調整することができる。一般的には、乾燥後の中間層の厚みは、３０μｍ～３５０μｍが好ましく、５０μｍ～２５０μｍがより好ましい。 The thickness of the intermediate layer can be appropriately adjusted according to the purpose. In general, the thickness of the intermediate layer after drying is preferably 30 μm to 350 μm, more preferably 50 μm to 250 μm.
　また、中間層には、さらに、成膜助剤、顔料、難燃剤、充填材、老化防止剤、紫外線吸収剤、芳香剤等の成分を添加することができる。
　なかでも、本開示の合成皮革が中間層を有する場合、中間層は難燃剤を含むことが好ましい。接着層と中間層との双方が難燃剤を含むことで、合成皮革の難燃性がより向上する。 Further, components such as film forming aids, pigments, flame retardants, fillers, anti-aging agents, ultraviolet absorbers, and fragrances can be added to the intermediate layer.
Especially, when the synthetic leather of this indication has an intermediate | middle layer, it is preferable that an intermediate | middle layer contains a flame retardant. When both the adhesive layer and the intermediate layer contain a flame retardant, the flame retardancy of the synthetic leather is further improved.
〔合成皮革の層構成〕
　本開示の合成皮革の層構成の例を、図を参照して説明する。
　図１は、本発明の合成皮革１０の一実施形態を示す概略断面図である。
　図１に示す実施形態の合成皮革（第１の実施形態と称することがある）１０は、既述の基布１２と、前記基布１２の一方の面上に、備えられた難燃剤を含む接着層１４、及び前記接着層１４の、基布１２と接する面とは反対側の面に、表皮層１６を備える。なお、本明細書において合成皮革１０が基布１２、接着層１４、及び表皮層１６を備えるとは、基布１２側から接着層１４と表皮層１６とがこの順に存在していること意味し、所望により設けられる他の層の存在を否定するものではない。 [Layer structure of synthetic leather]
An example of the layer configuration of the synthetic leather of the present disclosure will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an embodiment of the synthetic leather 10 of the present invention.
A synthetic leather (sometimes referred to as a first embodiment) 10 of the embodiment shown in FIG. 1 includes the base fabric 12 described above and a flame retardant provided on one surface of the base fabric 12. The skin layer 16 is provided on the adhesive layer 14 and the surface of the adhesive layer 14 opposite to the surface in contact with the base fabric 12. In this specification, that the synthetic leather 10 includes the base cloth 12, the adhesive layer 14, and the skin layer 16 means that the adhesive layer 14 and the skin layer 16 exist in this order from the base fabric 12 side. The existence of other layers provided as desired is not denied.
　本開示の合成皮革の製造方法には特に制限はなく、公知の製造方法を適宜適用することができる。
　以下、図１に示す如き層構成を有する合成皮革を例に挙げて、合成皮革の好ましい製造方法について説明する。 There is no restriction | limiting in particular in the manufacturing method of the synthetic leather of this indication, A well-known manufacturing method can be applied suitably.
Hereinafter, taking a synthetic leather having a layer structure as shown in FIG. 1 as an example, a preferred method for producing synthetic leather will be described.
〔表皮層の形成〕
　表皮層は、離型剤層を有する仮支持体の離型剤層表面に、樹脂、好ましくは、ポリウレタンを含む表皮層形成用組成物を、例えば、密閉式もしくは開放式コーティングヘッドにて塗布して表皮層形成用組成物層を形成し、形成された表皮層形成用組成物層を加熱乾燥して得ることができる。
　表皮層は、表皮層形成用組成物の処方、塗布量などを調整することにより、所望の厚みに形成させることができる。 [Formation of the skin layer]
For the skin layer, a composition for forming a skin layer containing a resin, preferably polyurethane, is applied to the surface of the release agent layer of the temporary support having a release agent layer, for example, with a sealed or open coating head. The skin layer forming composition layer can be formed, and the formed skin layer forming composition layer can be obtained by heating and drying.
The skin layer can be formed to a desired thickness by adjusting the formulation of the composition for forming the skin layer, the coating amount, and the like.
　表皮層の形成に用いられる仮支持体としては、表面に離型剤層を有し、表皮層を形成する側の表面には所望のシボ型（凹凸模様）が形成された仮支持体を挙げることができる。
　例えば、合成皮革を天然皮革様の外観を有する表皮層を備えるものとする場合には、予め仮支持体の離型剤層を形成する側の表面に皮革様の凹凸模様を形成すればよい。仮支持体として、表面に凹凸模様が形成された仮支持体用い、前記仮支持体の離型剤層が形成された側の表面に表皮層形成用組成物を塗布することで、形成される表皮層には仮支持体に予め形成された皮革様の凹凸模様が転写され、仮支持体を剥離した後、方面に凹凸模様を有する表皮層が形成される。
　なお、表皮層への凹凸模様の形成方法は、上記に限定されず、例えば、表皮層を含む複数の層を熱圧着する際にエンボス加工により凹凸模様を形成することもできる。
　表皮層形成用組成物に使用できるポリウレタンは既述の通りである。 Examples of the temporary support used for forming the skin layer include a temporary support having a release agent layer on the surface and a desired embossed pattern (uneven pattern) formed on the surface on which the skin layer is formed. be able to.
For example, when the synthetic leather is provided with a skin layer having a natural leather-like appearance, a leather-like uneven pattern may be formed in advance on the surface of the temporary support on the side where the release agent layer is formed. As a temporary support, it is formed by using a temporary support having a concavo-convex pattern formed on the surface, and applying a composition for forming a skin layer on the surface of the temporary support on which the release agent layer is formed. A leather-like uneven pattern formed in advance on the temporary support is transferred to the skin layer, and after peeling the temporary support, a skin layer having an uneven pattern in the direction is formed.
In addition, the formation method of the uneven | corrugated pattern to a skin layer is not limited above, For example, when thermocompression bonding the some layer containing a skin layer, an uneven | corrugated pattern can also be formed by embossing.
The polyurethane which can be used for the composition for forming the skin layer is as described above.
　表皮層の塗布量、及び膜厚には特に制限はなく、目的に応じて適宜選択される。一般的には、強度及び外観の観点から、表皮層の乾燥後の膜厚は、１０μｍ～５０μｍ程度が好ましく、１０μｍ～３０μｍ程度がより好ましい。 There is no particular limitation on the coating amount and film thickness of the skin layer, and it is appropriately selected according to the purpose. In general, from the viewpoint of strength and appearance, the thickness of the skin layer after drying is preferably about 10 μm to 50 μm, more preferably about 10 μm to 30 μm.
〔難燃剤を含む接着層の形成〕
　形成された表皮層の表面に接着層を設ける。接着層は表皮層の凹凸模様が形成された面とは反対側の面に設ける。 [Formation of adhesive layer containing flame retardant]
An adhesive layer is provided on the surface of the formed skin layer. The adhesive layer is provided on the surface opposite to the surface on which the uneven pattern of the skin layer is formed.
　仮支持体上に、表皮層を形成した後、表皮層の表面にポリウレタンと難燃剤とを含む接着層形成用組成物を、密閉式もしくは開放式コーティングヘッドにて塗工して接着層形成用組成物層を形成し、形成された接着層形成用組成物層を加熱乾燥して所望の厚みの接着層形成用塗布液層を形成する。
　その後、仮支持体上に、表皮層と、形成された接着層形成用組成物層とを有する積層体の、接着層形成用組成物層側と、既述の基布と、が接する向きに重ね合わせて熱圧着させ、接着層形成用組成物層に含まれる接着剤を反応硬化させて、接着層の形成と、接着層と基布との密着とを同時に行い、その後、仮支持体を剥離することで、合成皮革を得ることができる。 After forming the skin layer on the temporary support, the adhesive layer forming composition containing polyurethane and a flame retardant is applied to the surface of the skin layer with a sealed or open coating head to form the adhesive layer. A composition layer is formed, and the formed adhesive layer forming composition layer is heated and dried to form an adhesive layer forming coating liquid layer having a desired thickness.
Then, on the temporary support, in the direction in which the adhesive layer forming composition layer side of the laminate having the skin layer and the formed adhesive layer forming composition layer is in contact with the aforementioned base fabric Overlap and thermocompression bonding, the adhesive contained in the composition layer for forming the adhesive layer is reaction-cured, and the adhesive layer is formed and the adhesive layer and the base fabric are adhered at the same time. By peeling, synthetic leather can be obtained.
　接着層形成用組成物層を硬化させて接着層を形成する際の、硬化反応促進のための加熱温度及び加熱時間は、接着層形成用組成物に含まれる接着剤の種類により適宜選択される。一般的には加熱温度は３０℃～８０℃の範囲であることが好ましく、加熱時間は１２時間～７２時間の範囲であることが好ましい。
　加熱圧着を行う際は、ロールニップ装置等の公知の装置により、加熱温度を１００℃～１５０℃の範囲としてラミネートを行うことが好ましい。
　また、基布が少なくとも片面に起毛を有する場合、起毛を有する側を接着層形成用塗布液層と密着させることで、基布の起毛繊維が接着層形成用塗布液層に浸入し、その状態で接着層が硬化されることで、基布と接着層との密着性がより向上する。 When the adhesive layer forming composition layer is cured to form the adhesive layer, the heating temperature and heating time for promoting the curing reaction are appropriately selected depending on the type of adhesive contained in the adhesive layer forming composition. . In general, the heating temperature is preferably in the range of 30 ° C. to 80 ° C., and the heating time is preferably in the range of 12 hours to 72 hours.
When thermocompression bonding is performed, it is preferable to perform laminating by using a known apparatus such as a roll nip apparatus at a heating temperature in the range of 100 ° C. to 150 ° C.
In addition, when the base fabric has raised portions on at least one side, the raised fiber of the base fabric infiltrates into the adhesive layer forming coating liquid layer by bringing the raised side into close contact with the adhesive layer forming coating liquid layer. With the adhesive layer cured, the adhesion between the base fabric and the adhesive layer is further improved.
　既述の如く、好ましい合成皮革の製造方法の一例においては、仮支持体上に表皮層、及び接着層形成用組成物層の積層体を形成し、かつ、接着層と基布とは、接着層形成用組成物層の硬化により密着、固定化されたのち、離型層を有する仮支持体を剥離することで、弾力性、強度、及び難燃性が良好であり、燃焼時の発煙が抑制された合成皮革、例えば、図１に示す如き層構成の合成皮革を得ることができる。 As described above, in an example of a method for producing a preferable synthetic leather, a laminate of a skin layer and an adhesive layer forming composition layer is formed on a temporary support, and the adhesive layer and the base fabric are bonded. After adhering and fixing by curing the layer forming composition layer, the temporary support having a release layer is peeled off, and the elasticity, strength, and flame retardancy are good, and the smoke during combustion is Suppressed synthetic leather, for example, synthetic leather having a layer structure as shown in FIG. 1 can be obtained.
　図２は、本発明の別の実施形態の合成皮革（第２の実施形態と称することがある）２０を示す概略断面図である。
　第２の実施形態の合成皮革２０では、接着層１４と表皮層１６との間に、中間層１８を有する。合成皮革の使用態様に応じて、所望により接着層１４と表皮層１６との間に中間層１８を設けることで、合成皮革２０の弾力性、柔軟性、及び形状追随性等がより良好となる。 FIG. 2 is a schematic cross-sectional view showing a synthetic leather (sometimes referred to as a second embodiment) 20 according to another embodiment of the present invention.
In the synthetic leather 20 of the second embodiment, an intermediate layer 18 is provided between the adhesive layer 14 and the skin layer 16. Depending on the use mode of the synthetic leather, the elasticity, flexibility, shape followability, etc. of the synthetic leather 20 become better by providing the intermediate layer 18 between the adhesive layer 14 and the skin layer 16 as desired. .
〔中間層の形成〕
　中間層の構成には特に制限はない。強度と柔軟性の観点からはポリウレタンを含有する中間層が好ましい。 (Formation of intermediate layer)
There is no particular limitation on the structure of the intermediate layer. From the viewpoint of strength and flexibility, an intermediate layer containing polyurethane is preferred.
　中間層は、既述の如くして仮支持体上に表皮層を形成した後、表皮層の仮支持体とは反対側の面上に、好ましくはポリウレタンを含む中間層形成用組成物を塗布して、中間層形成用組成物層を形成し、形成された中間層形成用組成物層を、加熱乾燥して、仮支持体上に、表皮層と、中間層とを有する積層体を形成することができる。中間層形成用組成物の塗布及び加熱乾燥を２回以上繰り返すことで、任意の厚さの中間層を形成することもできる。 After forming the skin layer on the temporary support as described above, the intermediate layer is preferably coated with an intermediate layer forming composition containing polyurethane on the surface of the skin layer opposite to the temporary support. Then, the intermediate layer forming composition layer is formed, and the formed intermediate layer forming composition layer is heated and dried to form a laminate having a skin layer and an intermediate layer on the temporary support. can do. By repeating the application of the composition for forming an intermediate layer and heating and drying twice or more, an intermediate layer having an arbitrary thickness can be formed.
　中間層はクッション性向上などの目的で、気泡を内包するポリウレタン中間層であってもよい。気泡を内包するポリウレタン中間層の形成方法の一例を挙げて説明する。
　例えば、ポリウレタンを含有する中間層形成用組成物に、溶剤、増粘剤を適宜用いて粘度を調整し、撹拌して機械発泡させることで、気泡を内包したクリーム状の中間層形成用組成物を調製することができる。得られたクリーム状の中間層形成用組成物を、既述の表皮層上に塗布して気泡を内包する中間層形成用組成物層を形成し、これを乾燥硬化することで気泡を内包するポリウレタン中間層を形成することができる。
　機械発泡を行う中間層形成用組成物には、起泡剤、整泡剤、架橋剤、増粘剤等を含有させてもよい。 The intermediate layer may be a polyurethane intermediate layer containing bubbles for the purpose of improving cushioning properties. An example of a method for forming a polyurethane intermediate layer containing bubbles will be described.
For example, a composition for forming a creamy intermediate layer containing bubbles is prepared by adjusting the viscosity of a composition for forming an intermediate layer containing polyurethane as appropriate using a solvent and a thickener, and stirring and mechanically foaming the composition. Can be prepared. The obtained creamy intermediate layer forming composition is applied onto the above-described skin layer to form an intermediate layer forming composition layer that encloses bubbles, and this is dried and cured to enclose bubbles. A polyurethane interlayer can be formed.
The intermediate layer forming composition that performs mechanical foaming may contain a foaming agent, a foam stabilizer, a crosslinking agent, a thickener, and the like.
　通常のバッチ式撹拌機、例えばホバートミキサー、ホィッパーなどを用いることで、中間層形成用組成物を、空気を巻き込みながら機械的に撹拌することができ、クリーム状に機械発泡した中間層形成用組成物を得ることができる。量産化においては、オークスミキサー、ピンミキサーなどを用いて、定量の空気量を送り込みながら連続的に撹拌して、クリーム状に機械発泡した中間層形成用組成物を得る方法をとることができる。
　機械発泡させて得たクリーム状の中間層形成用組成物を表皮層上に塗布する際には、通常のナイフコーター、コンマコーター、ロールコーター、リップコーターなどの公知の塗工装置を使用することができる。 By using a normal batch stirrer, such as a Hobart mixer or a hopper, the intermediate layer forming composition can be mechanically stirred while entraining air, and the intermediate layer forming composition is mechanically foamed into a cream. You can get things. In mass production, a method of obtaining a composition for forming an intermediate layer which is mechanically foamed in a cream form by continuously stirring while feeding a predetermined amount of air using an oak mixer, a pin mixer or the like can be used.
When applying the creamy intermediate layer forming composition obtained by mechanical foaming onto the skin layer, use a known coating device such as a normal knife coater, comma coater, roll coater, lip coater, etc. Can do.
　また、気泡を内包するポリウレタン中間層の別の形成方法として、中間層形成用組成物に、熱膨張マイクロカプセル、４，４”－オキシビズ（ベンゼンスルホニルヒドラジド）、アゾジカルボンアミド、炭酸水素ナトリウム等の化学発泡剤を含有させ、既述の表皮層上に塗布し、その後、加熱乾燥して化学発泡剤を発泡させ、気泡を内包する中間層を形成する方法を挙げることができる。 Further, as another method for forming a polyurethane intermediate layer enclosing bubbles, the intermediate layer forming composition may include a thermally expanded microcapsule, 4,4 ″ -oxybiz (benzenesulfonyl hydrazide), azodicarbonamide, sodium hydrogen carbonate, and the like. Examples thereof include a method in which a chemical foaming agent is contained, applied onto the above-described skin layer, and then heated and dried to foam the chemical foaming agent to form an intermediate layer containing bubbles.
　形成された中間層の、表皮層とは反対側の面に、既述の第１の実施形態と同様にして、接着層形成用組成物を塗布して接着層形成用組成物層を形成し、形成された接着層形成用組成物層を有する面と基布とを密着させ、接着層形成用組成物層を硬化させ、その後、仮支持体を剥離することで、図２に示す層構成を有する合成皮革を得ることができる。 An adhesive layer forming composition layer is formed by applying an adhesive layer forming composition to the surface of the formed intermediate layer opposite to the skin layer in the same manner as in the first embodiment. The layer structure shown in FIG. 2 is obtained by closely adhering the surface having the formed adhesive layer forming composition layer and the base fabric, curing the adhesive layer forming composition layer, and then peeling the temporary support. A synthetic leather having the following can be obtained.
　化学発泡剤を用いる場合には、中間層形成用組成物に、化学発泡剤に加え、起泡剤、整泡剤、架橋剤、増粘剤等を含有させてもよい。 In the case of using a chemical foaming agent, the composition for forming an intermediate layer may contain a foaming agent, a foam stabilizer, a crosslinking agent, a thickener, and the like in addition to the chemical foaming agent.
　また、中間層形成用組成物には、さらに、成膜助剤、顔料、難燃剤、充填材、老化防止剤、紫外線吸収剤、芳香剤等の成分を添加することができる。 Further, components such as a film forming aid, a pigment, a flame retardant, a filler, an antiaging agent, an ultraviolet absorber, and an aromatic can be further added to the intermediate layer forming composition.
〔その他の層の形成〕
　本開示の合成皮革は、基布の少なくとも一方の面に備えられる既述の表皮層、接着層及び所望により設けられる中間層に加え、効果を損なわない限り、さらに、その他の層を設けてもよい。
　その他の層の一例である表面処理層の形成について以下に説明する。 [Formation of other layers]
The synthetic leather of the present disclosure may be further provided with other layers as long as the effect is not impaired in addition to the above-described skin layer, adhesive layer, and optionally provided intermediate layer provided on at least one surface of the base fabric. Good.
The formation of a surface treatment layer that is an example of other layers will be described below.
（表面処理層）
　表面処理層は、水系エマルジョン樹脂を含む表面処理剤組成物や有機溶剤系表面処理剤組成物を、既述の表皮層の表面に塗布することで形成することができる。
　表面処理層の形成に使用される樹脂には特に制限はなく、目的に応じていずれの樹脂を用いてもよい。表面処理層の形成に使用される樹脂としては、例えば、ポリウレタン、アクリル、エラストマー等が好ましく、ポリウレタンがより好ましい。
　表皮層表面に表面処理剤層を形成することで、合成皮革の外観がより良化する。
　表面処理層には、架橋剤、有機フィラー、滑剤、難燃剤等を含有させることができる。例えば、表面処理層に有機フィラー、滑剤等を含有することで、表皮材に滑らかな感触が付与され、耐摩耗性がより向上する。 (Surface treatment layer)
The surface treatment layer can be formed by applying a surface treatment agent composition containing an aqueous emulsion resin or an organic solvent surface treatment agent composition to the surface of the skin layer described above.
There is no restriction | limiting in particular in resin used for formation of a surface treatment layer, You may use any resin according to the objective. As the resin used for forming the surface treatment layer, for example, polyurethane, acrylic, elastomer and the like are preferable, and polyurethane is more preferable.
By forming the surface treatment agent layer on the surface of the skin layer, the appearance of the synthetic leather is improved.
The surface treatment layer can contain a crosslinking agent, an organic filler, a lubricant, a flame retardant, and the like. For example, when the surface treatment layer contains an organic filler, a lubricant, etc., a smooth feel is imparted to the skin material, and the wear resistance is further improved.
　本開示の合成皮革は、耐久性及び難燃性が良好であり、燃焼時の発煙が抑制された基布と難燃剤を含む接着層とを備えるため、耐久性及び難燃性が良好である。このため、自動車用内装材、鉄道車両内装部品、航空機内装部品、家具、靴、履物、鞄、建装用内外装部材、衣類表装材、衣類裏地など種々の分野に好適に使用することができ、シートや椅子などの複雑な立体形状を有する部材の表面を被覆するような場合においても、天然皮革を用いた場合と同様の感触と外観を達成することができるという効果をも奏する。 The synthetic leather of the present disclosure has good durability and flame retardancy, and includes a base fabric in which smoke generation during combustion is suppressed and an adhesive layer containing a flame retardant, and thus has good durability and flame retardancy. . For this reason, it can be suitably used in various fields such as automobile interior materials, railway vehicle interior parts, aircraft interior parts, furniture, shoes, footwear, bags, building interior and exterior members, clothing cover materials, clothing linings, Even in the case where the surface of a member having a complicated three-dimensional shape such as a seat or a chair is covered, the same feel and appearance as when natural leather is used can be achieved.
　以下、実施例を挙げて既述の実施形態をより具体的に説明するが、本発明は以下の実施例に制限されず、本発明の主旨を逸脱しない、限り種々の変型が可能である。 Hereinafter, the embodiments described above will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and various modifications can be made without departing from the gist of the present invention.
〔実施例１〕
　難燃繊維であるポリ塩化ビニリデン－アクリル共重合体繊維（ＬＯＩ値：３３）、セルロース系繊維であるレーヨン繊維（ＬＯＩ値：１９）、及び炭素系繊維であるフェノール系炭素繊維（ＬＯＩ値：３３）の３種の繊維を用いて紡糸して得た太さが２２番手の混紡糸を用いて、編み組織がモクロディであり厚みが０．９ｍｍ、重量が３１０ｇ／ｍ２の編製体（編物）を作製し、基布を得た。ポリ塩化ビニリデン繊維と、レーヨン繊維と、フェノール系炭素繊維との混紡率は、質量比で、３５：３５：３０であった。
　得られた基布のＪＩＳ　Ｋ７２０１（２００６年）により測定したＬＯＩ値は３７であった。
　仮支持体としては、表面離型処理され、離型層を有する紋付き離型紙（大日本印刷（株）製、ＤＥ－４１：紙厚平均１４０μｍを用いた。 [Example 1]
Polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33) which is a flame retardant fiber, rayon fiber (LOI value: 19) which is a cellulosic fiber, and phenolic carbon fiber (LOI value: 33) which is a carbon fiber. ) Using a 22-th blended yarn obtained by spinning using three types of fibers, a knitted fabric having a knitting structure of mokurodi, a thickness of 0.9 mm, and a weight of 310 g / m 2 (knitted fabric) A base fabric was obtained. The blend ratio of the polyvinylidene chloride fiber, the rayon fiber, and the phenolic carbon fiber was 35:35:30 in terms of mass ratio.
The LOI value measured by JIS K7201 (2006) of the obtained base fabric was 37.
As a temporary support, a cleaved release paper (Dai Nippon Printing Co., Ltd., DE-41: paper thickness average 140 μm) having a surface release treatment and having a release layer was used.
（表皮層形成用組成物）
・１００％モジュラスが５ＭＰａの無黄変型ポリカーボネート系ウレタン樹脂（ＤＩＣ（株）製、クリスボンＮＹ３２７：商品名）
　　　　　　　　　　　　　　　　　　　　　　　　　　１００質量部
・着色有機樹脂微粒子（ＤＩＣ（株）、ダイラック（登録商標）カラーシリーズ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　１８質量部
・溶剤（Ｎ，Ｎ－ジメチルホルムアミド（ＤＭＦ）と、イソプロパノール（ＩＰＡ）との質量比　８０：２０の混合溶媒）
　　　　　　　　　　　　　　　　　　　　　　　　　　　３６質量部 (Skin layer forming composition)
・ 100% modulus 5MPa non-yellowing polycarbonate urethane resin (DIC Corporation, Crisbon NY327: trade name)
100 parts by mass, colored organic resin fine particles (DIC Corporation, Dirac (registered trademark) color series)
18 parts by mass / solvent (mixed solvent of N, N-dimethylformamide (DMF) and isopropanol (IPA) at a mass ratio of 80:20)
36 parts by mass
　上記表皮層形成用組成物を充分に混合し、表皮層形成用組成物を得た。
　前記離型層を備えた仮支持体の離型層形成側の表面に、前記表皮層形成用組成物を、開放式のコーティングヘッド塗工装置を用いて、乾燥後の膜厚が約３０μｍとなる量で塗布し、１００℃で２分間、熱風乾燥機を用いて塗膜を熱風乾燥して、仮支持体上に表皮層を形成した。得られた表皮層を目視にて観察したところ、ピンホールのない均一な表皮層であった。 The composition for forming a skin layer was sufficiently mixed to obtain a composition for forming a skin layer.
On the surface on the release layer forming side of the temporary support provided with the release layer, the composition for forming the skin layer is about 30 μm after drying using an open type coating head coating apparatus. The coating film was dried with hot air using a hot air dryer at 100 ° C. for 2 minutes to form a skin layer on the temporary support. When the obtained skin layer was observed visually, it was a uniform skin layer without a pinhole.
（接着層形成用組成物）
・１００％モジュラスが２．５ＭＰａの難黄変型ポリカーボネート系ポリウレタン接着剤（ＤＩＣ（株）製、クリスボンＴＡ２０５ＦＴ：商品名）
　　　　　　　　　　　　　　　　　　　　　　　　　　１００質量部
・非デカブロ系ハロゲン系難燃剤（アンチモン併用型）　　２０質量部
　（丸菱油化工業（株）製、ノンネン（登録商標）ＳＡＮ－２：商品名）
・溶剤（ＤＭＦと、メチルエチルケトン（ＭＥＫ）との質量比　８５：１５の混合溶媒）
　　　　　　　　　　　　　　　　　　　　　　　　　　　６５質量部
　・架橋剤（ＤＩＣ（株）製、バーノック（登録商標）ＤＮ９５０：商品名）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１０質量部 (Adhesive layer forming composition)
・ Hard yellowing-type polycarbonate polyurethane adhesive with 100% modulus of 2.5 MPa (made by DIC Corporation, Crisbon TA205FT: trade name)
100 parts by mass / non-decabro halogen-based flame retardant (antimony combined type) 20 parts by mass (manufactured by Maruhishi Oil Chemical Co., Ltd., Nonnen (registered trademark) SAN-2: trade name)
・ Solvent (mixed solvent with a mass ratio of DMF and methyl ethyl ketone (MEK) of 85:15)
65 parts by mass-Crosslinking agent (manufactured by DIC Corporation, Bernock (registered trademark) DN950: trade name)
10 parts by mass
　上記接着層形成用組成物の各成分を充分に混合し、接着層形成用組成物を得た。
　仮形成した表皮層の仮支持体とは反対側の面上に、接着層形成用組成物を乾燥後の厚みが５０μｍとなる量で開放式のコーティングヘッドを用いて塗工し、１００℃で２分間乾燥して、接着層形成用塗布液層を形成し、合成皮革形成用の積層体を得た。 The components of the adhesive layer forming composition were sufficiently mixed to obtain an adhesive layer forming composition.
On the surface opposite to the temporary support of the temporarily formed skin layer, the adhesive layer forming composition was applied using an open-type coating head in an amount such that the thickness after drying was 50 μm, at 100 ° C. It dried for 2 minutes, the coating liquid layer for contact bonding layer formation was formed, and the laminated body for synthetic leather formation was obtained.
　次に、得られた合成皮革形成用の積層体の、接着層形成用塗布液層と基布とを接触させ、ニップ装置でラミネートしたのち、巻き取って５０℃で４８時間維持し、接着層形成用塗布液層に含まれる接着剤の硬化反応を進行させ、基布と密着した接着層を形成した。
　その後、仮支持体を剥離して、基布表面に、接着層及び表皮層をこの順で有する実施例１の合成皮革を得た。
　得られた実施例１の合成皮革を目視で観察したところ、シボ転写不良による柄抜けがなく、外観に優れ、指で押した場合の弾力性、感触は良好であった。 Next, the obtained layered product for forming synthetic leather was brought into contact with the coating liquid layer for forming the adhesive layer and the base fabric, laminated with a nip device, wound up, and maintained at 50 ° C. for 48 hours. The curing reaction of the adhesive contained in the forming coating liquid layer was advanced to form an adhesive layer in close contact with the base fabric.
Thereafter, the temporary support was peeled off to obtain the synthetic leather of Example 1 having an adhesive layer and a skin layer in this order on the surface of the base fabric.
When the obtained synthetic leather of Example 1 was visually observed, there was no pattern loss due to imperfect transfer on the surface, the appearance was excellent, and the elasticity and feel when pressed with a finger were good.
［実施例２］
　実施例１と同様にして、離型紙上に表皮層を仮形成した。
　次に、下記処方の成分を充分に混合し、中間層形成用組成物を調製した。
（中間層形成用組成物）
・１００％モジュラスが５ＭＰａの難黄変型ポリカーボネート系ウレタン樹脂（ＤＩＣ（株）製、クリスボンＴＫ１０１５Ｔ）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　１００質量部
　
・熱膨張ビーズ　　　　　　　　　　　　　　　　　　　　　　　４質量部
　（日本フェライト（株）製、エクスパンセル９２０ＤＵ１２０）
・アミン系鎖長剤　　　　　　　　　　　　　　　　　　　　４．６質量部
　（ＢＡＳＦジャパン（株）製、ラロミン（登録商標）Ｃ２６０）
・着色有機樹脂微粒子　　　　　　　　　　　　　　　　　　　　５質量部
　（ＤＩＣ（株）製、ダイラックカラーシリーズ）
・リン系難燃剤（アークロマジャパン（株）製、ＰＥＫＯＦＬＡＭ（登録商標）　ＡＴＣパウダー）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　　３０質量部
・溶剤（ＤＭＦと１-メトキシ－２プロパノール（ＰＧＭ）と酢酸エチルとの質量比：２４：３８：３８の混合溶媒）
　　　　　　　　　　　　　　　　　　　　　　　　　　　　５２質量部 [Example 2]
In the same manner as in Example 1, a skin layer was temporarily formed on the release paper.
Next, components of the following formulation were sufficiently mixed to prepare an intermediate layer forming composition.
(Composition for intermediate layer formation)
・ Hard yellowing polycarbonate urethane resin with 100% modulus of 5 MPa (DIC Corporation, Crisbon TK1015T)
100 parts by weight
-Thermal expansion beads 4 parts by mass (Nippon Ferrite Co., Ltd., Expandel 920DU120)
-4.6 part by weight of an amine chain extender (BASF Japan, Lalomin (registered trademark) C260)
・ Colored organic resin fine particles 5 parts by mass (DIC Corporation, Dirac Color Series)
・ Phosphorus flame retardant (Acroma Japan Co., Ltd., PEKOFLAM (registered trademark) ATC powder)
30 parts by mass / solvent (mass ratio of DMF, 1-methoxy-2-propanol (PGM) and ethyl acetate: mixed solvent of 24:38:38)
52 parts by mass
　既述の仮形成した表皮層の、仮支持体とは反対側の面上に、得られた中間層形成用組成物を、開放式のコーティング塗工装置を用いて、乾燥後の膜厚が２００μｍとなる量で塗布し、１７０℃で２分間、熱風乾燥機を用いて塗膜を熱風乾燥して、熱膨張ビーズを膨張させ、表皮層上に、気泡を内包する中間層を形成した。
　形成された中間層の表皮層とは反対側の面上に、実施例１と同様にして接着層形成用塗布液層を形成し、合成皮革形成用の積層体を得た。
　次に、得られた合成皮革形成用の積層体の、接着層形成用塗布液層と、実施例１で用いたものと同じ基布とを接触させ、接着層形成用塗布液層の乾燥後、熱圧着により基布と密着させた。このようにして、実施例１の合成皮革に、さらに気泡を内包する中間層を備えた実施例２の合成皮革を得た。
　得られた実施例２の合成皮革は、外観に優れ、指で押した場合の弾力性、感触は実施例１の合成皮革よりもさらに良好であった。 On the surface of the previously-formed temporarily formed skin layer on the side opposite to the temporary support, the obtained intermediate layer-forming composition is subjected to a film thickness after drying using an open coating coating apparatus. The coating was applied in an amount of 200 μm, and the coating film was dried with hot air using a hot air dryer at 170 ° C. for 2 minutes to expand the thermally expanded beads, thereby forming an intermediate layer containing bubbles on the skin layer.
A coating liquid layer for forming an adhesive layer was formed on the surface of the formed intermediate layer opposite to the skin layer in the same manner as in Example 1 to obtain a laminate for forming synthetic leather.
Next, the obtained layered product for forming synthetic leather is brought into contact with the coating layer for forming the adhesive layer and the same base fabric as used in Example 1, and after drying the coating layer for forming the adhesive layer Then, it was adhered to the base fabric by thermocompression bonding. In this way, the synthetic leather of Example 2 provided with the intermediate layer containing the bubbles in the synthetic leather of Example 1 was obtained.
The obtained synthetic leather of Example 2 was excellent in appearance, and the elasticity and feel when pressed with a finger were even better than those of Example 1.
［比較例１］
　実施例１において用いた基布に代えて、難燃繊維であるポリ塩化ビニリデン－アクリル共重合体繊維（ＬＯＩ値：３３）及びセルロース系繊維であるレーヨン繊維（ＬＯＩ値：１９）の２種の繊維を、質量比で６５：３５の割合で用いて紡糸して得た２２番手の混紡糸を用いて、実施例１における基布と同様の編製で基布を得て、得られた基布を用いた以外は実施例１と同様にして、比較例１の合成皮革を製造した。 [Comparative Example 1]
In place of the base fabric used in Example 1, two types of fibers, a flame retardant polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33) and a cellulosic rayon fiber (LOI value: 19), were used. A base fabric was obtained by knitting the same as the base fabric in Example 1, using a 22nd blended yarn obtained by spinning fibers at a mass ratio of 65:35. A synthetic leather of Comparative Example 1 was produced in the same manner as in Example 1 except that was used.
［比較例２］
　実施例１において用いた基布に代えて、難燃繊維であるポリ塩化ビニリデン－アクリル共重合体繊維（ＬＯＩ値：３３）のみからなる２２番手の糸を用いて、実施例１における基布と同様の編製で基布を得て、得られた基布を用いた以外は実施例１と同様にして、比較例２の合成皮革を製造した。 [Comparative Example 2]
In place of the base fabric used in Example 1, 22th yarn consisting only of a polyvinylidene chloride-acrylic copolymer fiber (LOI value: 33), which is a flame retardant fiber, was used. A synthetic leather of Comparative Example 2 was produced in the same manner as in Example 1 except that a base fabric was obtained by the same knitting and the obtained base fabric was used.
（得られた合成皮革の評価）
　得られた合成皮革について、以下の方法で評価した。結果を下記表１に示す。
１．難燃性評価
　得られた各合成皮革について、耐空性審査要領第III部　付録Ｆ垂直法に準拠して燃焼試験を行い、以下に示す基準１－１～１－３にて、難燃性を評価した。
　下記１－１～１－３の基準により、全ての項目でＡランクの場合、難燃性をＡと評価し、２つの項目でＡランクであり、且つ、不合格レベルのランクがない場合、難燃性をＢと評価した。表１に示す難燃性がＡ又はＢと評価された場合、実用上充分な難燃性を示すものと判断する。
１－１．燃焼時間
　着火してから燃焼が継続される時間を計測した。基準では、１５秒以内に燃焼が停止するものが合格とされている。
Ａ：燃焼時間が５秒以内
Ｂ：燃焼時間が５秒を超え、１０秒以内
Ｃ：燃焼時間が１０秒を超え、１５秒以内
Ｄ：燃焼時間が１５秒を超える（不合格レベル） (Evaluation of the synthetic leather obtained)
The obtained synthetic leather was evaluated by the following method. The results are shown in Table 1 below.
1. Flame retardant evaluation Each synthetic leather obtained was subjected to a flame test according to Part III Appendix F Vertical Method of Airworthiness Examination Guidelines, and flame retardant was evaluated according to the criteria 1-1 to 1-3 shown below. evaluated.
According to the criteria of 1-1 to 1-3 below, when all items are A ranks, the flame retardancy is evaluated as A, and two items are A ranks, and there is no rank of failure level, Flame retardancy was evaluated as B. When the flame retardancy shown in Table 1 is evaluated as A or B, it is judged that the flame retardance is practically sufficient.
1-1. Combustion time The time for which combustion continued after ignition was measured. According to the standard, a sample that stops combustion within 15 seconds is accepted.
A: Combustion time within 5 seconds B: Combustion time over 5 seconds and within 10 seconds C: Combustion time over 10 seconds, within 15 seconds D: Combustion time over 15 seconds (failed level)
１－２．燃焼長
　着火場所から燃焼が広がる長さを測定した。基準では、２０ｃｍ以内が合格とされている。
Ａ：燃焼長が１５ｃｍ以内
Ｂ：燃焼長が１５ｃｍを超え、２０ｃｍ以内
Ｃ：燃焼長が２０ｃｍを超える（不合格レベル） 1-2. Combustion length The length of combustion spread from the ignition location was measured. According to the standard, 20 cm or less is accepted.
A: Combustion length within 15 cm B: Combustion length exceeds 15 cm, within 20 cm C: Combustion length exceeds 20 cm (failure level)
１－３．落下物の燃焼時間
　着火した箇所からの落下物の燃焼が継続される時間を計測した。基準では、５秒以内に燃焼が停止するものが合格とされている。
Ａ：落下物が燃焼せず、直ちに燃焼が停止する
Ｂ：落下物の燃焼時間が５秒以内
Ｃ：落下物の燃焼時間が５秒を超える（不合格レベル） 1-3. Falling object burning time The time for which falling object combustion from the ignited point was continued was measured. According to the standard, a sample that stops combustion within 5 seconds is accepted.
A: Falling object does not burn, combustion stops immediately B: Combustion time of falling object within 5 seconds C: Combustion time of falling object exceeds 5 seconds (failed level)
２．発煙性試験
　合成皮革の発煙性試験を、スモークチャンバーを用いて、ＢＳＳ　７２３８　有炎法（航空機内装材の煙比光学密度測定　Boeing社規格）に準じて測定し、以下の基準にて評価した。発煙濃度が１００以下であることで、実用に供し得る発煙性であると評価する。
（評価基準）
Ａ：発煙濃度が８０以下である
Ｂ：発煙濃度が８０を超え、１００以下である
Ｃ：発煙濃度が１００を超える 2. Smoke test The smoke test of synthetic leather was measured using a smoke chamber according to the BSS 7238 flaming method (measurement of smoke specific optical density of aircraft interior materials Boeing standard) and evaluated according to the following criteria. When the smoke generation concentration is 100 or less, it is evaluated that the smoke generation property can be practically used.
(Evaluation criteria)
A: Smoke density is 80 or less B: Smoke density exceeds 80, 100 or less C: Smoke density exceeds 100
３．延焼防止性
　燃焼時に合成皮革の基布が溶融し、基布に穴が開くと、合成皮革の接着層、中間層等に用いられるポリウレタンなどの燃焼が促進されることから、合成皮革の表皮層側から燃焼試験を行ない、燃焼時において基布に穴が開くか否かを評価した。
（評価基準）
Ａ：基布の燃焼箇所が炭化し、穴が開かない
Ｂ：基布の燃焼箇所が溶融し、穴が開く（不合格レベル） 3. Fire spread prevention When the base fabric of synthetic leather melts and a hole is made in the base fabric during combustion, the combustion of polyurethane, etc., used in the adhesive layer and intermediate layer of synthetic leather is accelerated, so the skin layer of synthetic leather A combustion test was performed from the side, and it was evaluated whether or not a hole was formed in the base fabric during combustion.
(Evaluation criteria)
A: Combustion site of base fabric is carbonized and no hole is opened B: Combustion site of base fabric is melted and a hole is opened (failed level)
４．耐傷性
　合成皮革の表皮層側の耐傷性は、テーバースクラッチテスター（テスター産業（株）製、ＨＡ－２０１）を用いて、ＪＩＳ　Ｋ６２５３（２００６年）に記載の方法に準拠して試験を行い、以下の基準にて評価した。耐スクラッチ性の必要性能は２．９４Ｎ以上である。
（評価基準）
Ａ：２．９４Ｎ以上であった
Ｂ：２．９４Ｎ未満であった 4). Scratch resistance The scratch resistance on the skin layer side of synthetic leather was tested in accordance with the method described in JIS K6253 (2006) using a Taber Scratch Tester (manufactured by Tester Sangyo Co., Ltd., HA-201). Evaluation was made according to the following criteria. The required performance for scratch resistance is 2.94N or more.
(Evaluation criteria)
A: 2.94N or more B: Less than 2.94N
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果より、実施例１及び実施例２の合成皮革は、難燃性、延焼防止性及び耐傷性のいずれにも優れ、燃焼時の発煙が抑制され、燃焼時における視界の確保が期待できることがわかる。このため、難燃性と耐久性とが要求される航空機のシート材、車両用内装材、家具などに好適に使用し得ることがわかる。
　他方、基布として難燃繊維とセルロース系繊維を用いた比較例１の合成皮革は、燃焼時の発煙の抑制について実施例よりもやや劣り、難燃繊維のみを用いた比較例２は、実施例１に比較して延焼防止性が低く、発煙性も実用上問題となるレベルであった。 From the results in Table 1, the synthetic leathers of Examples 1 and 2 are excellent in all of flame retardancy, fire spread prevention and scratch resistance, smoke generation during combustion is suppressed, and visibility during combustion is expected to be ensured. I understand that I can do it. For this reason, it turns out that it can be used conveniently for the sheet | seat material of aircraft, the interior material for vehicles, furniture, etc. for which a flame retardance and durability are requested | required.
On the other hand, the synthetic leather of Comparative Example 1 using flame retardant fibers and cellulosic fibers as the base fabric is slightly inferior to the Examples in terms of suppressing smoke generation during combustion, and Comparative Example 2 using only flame retardant fibers was carried out. Compared with Example 1, the fire spread prevention property was low, and the smoke generation property was at a level causing a practical problem.
　２０１６年１２月２６日に出願された日本国特許出願２０１６－２５１７０６の開示は参照により本明細書に取り込まれる。
　本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。 The disclosure of Japanese Patent Application No. 2016-251706 filed on Dec. 26, 2016 is incorporated herein by reference.
All documents, patent applications, and technical standards mentioned in this specification are to the same extent as if each individual document, patent application, and technical standard were specifically and individually stated to be incorporated by reference, Incorporated herein by reference.

Claims (6)

  1. 　限界酸素指数が２５以上の難燃繊維と、セルロース系繊維と、炭素繊維とを含む糸の編製体であり、かつ、限界酸素指数が２５以上である基布と、
    　前記基布の少なくとも一方の面上に備えられる難燃剤を含む接着層と、
    　前記接着層の、前記基布側の面とは反対の面に備えられる表皮層と、を有する合成皮革。     A base fabric having a limiting oxygen index of 25 or more, which is a knitted fabric of a yarn including a flame retardant fiber having a limiting oxygen index of 25 or more, a cellulosic fiber, and a carbon fiber;
    An adhesive layer containing a flame retardant provided on at least one surface of the base fabric;
    A synthetic leather having a skin layer provided on a surface of the adhesive layer opposite to the surface on the base fabric side.
  2. 　前記難燃繊維が、アラミド繊維、メタ系アラミド繊維、ポリフェニレンサルファイド繊維、アクリル繊維、塩化ビニル繊維、ポリクラール繊維、塩化ビニリデン繊維、アクリル－塩化ビニル共重合体繊維、及びアクリル－塩化ビニリデン共重合体繊維、ポリベンゾイミダゾール繊維から選ばれた１種以上を含む請求項１に記載の合成皮革。 The flame retardant fiber is an aramid fiber, a meta-aramid fiber, a polyphenylene sulfide fiber, an acrylic fiber, a vinyl chloride fiber, a polyclar fiber, a vinylidene chloride fiber, an acrylic-vinyl chloride copolymer fiber, or an acrylic-vinylidene chloride copolymer fiber. The synthetic leather according to claim 1, comprising at least one selected from polybenzimidazole fibers.
  3. 　前記炭素繊維が、ポリアクリロニトリル系繊維、ピッチ系繊維、及びフェノール系繊維から選ばれた１種以上を含む請求項１又は請求項２に記載の合成皮革。 The synthetic leather according to claim 1 or 2, wherein the carbon fiber includes one or more selected from polyacrylonitrile fiber, pitch fiber, and phenol fiber.
  4. 　前記編製体を構成する糸の全質量に対する前記炭素繊維の含有量が２０質量％～４０質量％であり、前記編製体を構成する糸の全質量に対する前記セルロース系繊維の含有量が２５質量％～４５質量％であり、かつ、前記難燃繊維と前記炭素繊維の総含有量が、前記セルロース系繊維の含有量よりも多い請求項１～請求項３のいずれか１項に記載の合成皮革。 The carbon fiber content is 20% by mass to 40% by mass with respect to the total mass of the yarn constituting the knitted body, and the cellulosic fiber content is 25% by mass with respect to the total mass of the yarn constituting the knitted body. The synthetic leather according to any one of claims 1 to 3, wherein the synthetic leather has a total content of the flame retardant fiber and the carbon fiber that is higher than the content of the cellulosic fiber. .
  5. 　前記接着層と、前記表皮層との間に、さらに、中間層を備える請求項１～請求項４のいずれか１項に記載の合成皮革。 The synthetic leather according to any one of claims 1 to 4, further comprising an intermediate layer between the adhesive layer and the skin layer.
  6. 　前記中間層が、難燃剤を含有する請求項５に記載の合成皮革。 The synthetic leather according to claim 5, wherein the intermediate layer contains a flame retardant.
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