WO2018123290A1 - Cuir synthétique - Google Patents

Cuir synthétique 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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WIPO (PCT)
Prior art keywords
fiber
synthetic leather
layer
flame retardant
base fabric
Prior art date
Application number
PCT/JP2017/040468
Other languages
English (en)
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 US16/469,249 priority Critical patent/US20190382953A1/en
Priority to CN201780076655.9A priority patent/CN110073053B/zh
Priority to JP2018558877A priority patent/JP6895458B2/ja
Publication of WO2018123290A1 publication Critical patent/WO2018123290A1/fr

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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0009—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
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0015—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using fibres of specified chemical or physical nature, e.g. natural silk
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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
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    • D06N3/0038—Polyolefin fibres
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    • D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
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    • 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
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    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
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    • 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
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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    • 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
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    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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    • 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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    • D06N2209/00—Properties of the materials
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    • 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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un cuir synthétique comportant: un tissu de base qui est tricoté à partir d'un fil qui comprend une fibre ignifuge ayant un indice limite d'oxygène égal ou supérieur à 25, une fibre cellulosique et une fibre de carbone, le tissu de base ayant un indice limite d'oxygène égal ou supérieur à 25; une couche adhésive comprenant un agent ignifuge et disposée sur au moins une surface du tissu de base; et une couche la plus extérieure disposée sur la surface de la couche adhésive qui est en face de la surface en contact avec le tissu de base.
PCT/JP2017/040468 2016-12-26 2017-11-09 Cuir synthétique WO2018123290A1 (fr)

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US16/469,249 US20190382953A1 (en) 2016-12-26 2017-11-09 Synthetic leather
CN201780076655.9A CN110073053B (zh) 2016-12-26 2017-11-09 合成皮革
JP2018558877A JP6895458B2 (ja) 2016-12-26 2017-11-09 合成皮革

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WO2020116303A1 (fr) * 2018-12-05 2020-06-11 Dic株式会社 Composition de résine d'uréthane et cuir synthétique
JP2021025142A (ja) * 2019-08-01 2021-02-22 株式会社帝健 合成皮革用基布および合成皮革
US20210060910A1 (en) * 2018-02-22 2021-03-04 Alice ZANTEDESCHI Process for the manufacture of a membrane adapted for coupling to a fabric, and product so obtained
WO2022185689A1 (fr) * 2021-03-03 2022-09-09 セーレン株式会社 Cuir synthétique
EP3960926A4 (fr) * 2019-04-25 2023-02-15 Toray Industries, Inc. Cuir synthétique et article revêtu

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US20210060910A1 (en) * 2018-02-22 2021-03-04 Alice ZANTEDESCHI Process for the manufacture of a membrane adapted for coupling to a fabric, and product so obtained
US11794455B2 (en) * 2018-02-22 2023-10-24 Alice ZANTEDESCHI Process for the manufacture of a membrane adapted for coupling to a fabric, and product so obtained
CN109056352A (zh) * 2018-09-29 2018-12-21 世联汽车内饰（苏州）有限公司 一种难燃仿麂皮革及其制备方法
WO2020116303A1 (fr) * 2018-12-05 2020-06-11 Dic株式会社 Composition de résine d'uréthane et cuir synthétique
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JP7337588B2 (ja) 2019-08-01 2023-09-04 株式会社帝健 合成皮革用基布および合成皮革
WO2022185689A1 (fr) * 2021-03-03 2022-09-09 セーレン株式会社 Cuir synthétique

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CN110073053B (zh) 2022-05-03
JPWO2018123290A1 (ja) 2019-10-31

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