WO2012077180A1 - 自動車内装材用合成皮革 - Google Patents

自動車内装材用合成皮革 Download PDF

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Publication number
WO2012077180A1
WO2012077180A1 PCT/JP2010/071894 JP2010071894W WO2012077180A1 WO 2012077180 A1 WO2012077180 A1 WO 2012077180A1 JP 2010071894 W JP2010071894 W JP 2010071894W WO 2012077180 A1 WO2012077180 A1 WO 2012077180A1
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WIPO (PCT)
Prior art keywords
synthetic leather
layer
less
automobile interior
fine particles
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PCT/JP2010/071894
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English (en)
French (fr)
Japanese (ja)
Inventor
松井　まり子
石丸　園子
鶴海　英幸
Original Assignee
東洋紡績株式会社
日本エクスラン工業株式会社
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Application filed by 東洋紡績株式会社, 日本エクスラン工業株式会社 filed Critical 東洋紡績株式会社
Priority to CN201080003258.7A priority Critical patent/CN102741090B/zh
Priority to PCT/JP2010/071894 priority patent/WO2012077180A1/ja
Priority to KR1020137017627A priority patent/KR101571613B1/ko
Publication of WO2012077180A1 publication Critical patent/WO2012077180A1/ja

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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
    • D06N3/0056—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
    • D06N3/0068—Polymeric granules, particles or powder, e.g. core-shell particles, microcapsules
    • 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
    • D06N2209/00—Properties of the materials
    • D06N2209/12—Permeability or impermeability properties
    • D06N2209/126—Permeability to liquids, absorption
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/26—Vehicles, transportation
    • D06N2211/261—Body finishing, e.g. headliners
    • 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
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather

Definitions

  • the present invention relates to a synthetic leather for automobile interior materials, which is a synthetic leather, but suppresses an increase in the humidity level in the palm of the same level as that of genuine leather, has as little stickiness as genuine leather, and has a smooth feel.
  • Synthetic leather commonly used for automobile interior materials so-called PVC leather, is excellent in leather-like appearance, price, wear resistance, moldability, etc., and is currently used in vehicles, especially automobile interior materials such as the masses. It is widely used as a car roof material, door trim material, instrument panel material, car seat skin material, and the like.
  • PVC leather is composed of polyvinyl chloride, there is a concern about the generation of dioxins during incineration after disposal, and its use is being restricted due to the recent increase in environmental problems.
  • Synthetic leather other than PVC leather is also being studied.
  • an artificial leather having a skin layer formed of a synthetic resin on a base material layer such as a nonwoven fabric and having at least one layer containing moisture-absorbing / releasing moisture-absorbing exothermic fiber or moisture-absorbing / releasing moisture-absorbing exothermic powder (patent Reference 1 (see claim 1)); synthetic leather in which a synthetic resin layer containing sericin is laminated on a fibrous base (see patent document 2 (claim 1)); a thermoplastic polyurethane elastomer foam layer and heat Synthetic leather in which non-foamed layers of plastic polyurethane elastomer are sequentially provided (refer to Patent Document 3 (Claim 1)); a non-woven fabric base material formed by entanglement of a synthetic fiber web containing a metal-plated synthetic fiber; Synthetic leather impregnated and foamed with a polyurethane resin containing powder (see Patent Document 4 (Claim 1)); having a predetermined tensile tensile
  • the object of the present invention is to solve the above-mentioned conventional problems, and although it is a synthetic leather, it suppresses the rise level of the humidity in the palm to the same level as that of genuine leather, and is less sticky than genuine leather. It is to provide a synthetic leather for automobile interior materials having a tactile sensation.
  • the synthetic leather for automobile interior materials of the present invention is a synthetic leather in which a resin layer composed of a single layer or a multilayer synthetic resin is formed on a base layer of a nonwoven fabric or woven or knitted fabric having a single layer or a multilayer structure,
  • the resin layer contains hygroscopic fine particles, and the palm humidity rise ( ⁇ H) 1 minute after the start of sweating is 20% RH or less in the measurement of palm moisture using a sweat simulation apparatus for synthetic leather. And there is little stickiness and a synthetic leather having a smooth feel can be obtained.
  • the outermost layer of the resin layer preferably contains hygroscopic fine particles.
  • the feeling of stickiness of the synthetic leather can be further reduced, and the smooth feel can be imparted to the synthetic leather.
  • the synthetic leather of the present invention preferably has an average surface friction coefficient (MIU) of 0.25 or less at a load of 1.47 N / cm 2 . If the average surface friction coefficient is within the above range, the smoothness of the synthetic leather will be more excellent.
  • MIU average surface friction coefficient
  • the average particle diameter of the hygroscopic fine particles is preferably 1 ⁇ m or more and 50 ⁇ m or less.
  • the content of the hygroscopic fine particles of the resin layer is preferably 2 g / m 2 or more 50 g / m 2 or less.
  • the hygroscopic fine particles those using 50% by mass or more of an acrylic crosslinked polymer as a raw material are suitable.
  • the base material layer is a nonwoven fabric having a two-layer structure in which a fiber structure constituting an upper layer and a fiber structure constituting a lower layer are laminated by mechanical entanglement, and the basis weight of the upper layer is 40 g / m 2 or more 150 g / m 2 or less, the fineness of the fibers constituting the upper layer is 0.0001 dtex or more and 0.5 dtex or less, the basis weight of the lower layer is 40 g / m 2 or more and 200 g / m 2 or less, and the fineness of the fibers constituting the lower layer is 1 It is preferably 5 dtex or more and 10.0 dtex or less.
  • the nonwoven fabric When the substrate layer is a nonwoven fabric having a single layer or a multilayer structure, the nonwoven fabric has a density of 120 kg / m 3 or more and 250 kg / m 3 or less, a burst strength of 400 N or more and 1000 N or less, and a bending resistance of 1 mm or more. It is preferable that it is 120 mm or less.
  • the resin layer contains hygroscopic fine particles, and in the measurement of the internal humidity of the synthetic leather by using a sweating simulation apparatus, the increase in the internal humidity after 1 minute of the start of sweating is 20. Since it is suppressed to not more than% RH, there is little stickiness as with genuine leather, and a smooth feel can be realized.
  • the synthetic leather for automobile interior materials of the present invention is a synthetic leather in which a resin layer composed of a single layer or a multilayer synthetic resin is formed on a base layer of a nonwoven fabric or woven or knitted fabric having a single layer or a multilayer structure,
  • a resin layer composed of a single layer or a multilayer synthetic resin
  • the resin layer contains hygroscopic fine particles and the moisture content in the palm of the synthetic leather is measured by a sweating simulation device
  • ⁇ H the increase in the moisture content in the palm
  • multilayer means two or more layers.
  • the applicant used a sweating simulation device test method (skin model test method) and examined the correspondence with practical use.
  • the resin layer contains hygroscopic fine particles, and the increase in palm humidity ( ⁇ H) 1 minute after the start of sweating in the measurement of palm humidity with a sweating simulation device is suppressed to 20% RH or less, thereby making it sticky.
  • ⁇ H palm humidity
  • the skin model test method is a model evaluation method considering a practical environment in which constant water vapor and heat are always supplied to the surface layer of the synthetic leather.
  • This evaluation method uses a sweating simulation measuring device (manufactured by Toyobo Co., Ltd.), water supply amount: 140 g / m 2 ⁇ h, hot plate temperature: 37 ° C., sample-hot plate distance: 0.5 cm, environmental temperature and humidity : 20 ° C. ⁇ 65% RH, sweat pattern: sweating is carried out for 5 minutes from the start of the test, and the temperature and humidity of the space between the hot plate and the sample (synthetic leather) are measured.
  • the ⁇ H of the synthetic leather for automobile interior materials of the present invention is 20% RH or less, preferably 18% RH or less, more preferably 16% RH or less. When the ⁇ H exceeds 20% RH, the feeling of stickiness of the synthetic leather for automobile interior materials becomes poor.
  • the lower limit of ⁇ H is not particularly limited, but is 0% RH.
  • the average surface friction coefficient (MIU) at 1.47 kgf / cm 2 load of the synthetic leather for automobile interior materials is preferably 0.25 or less, more preferably 0.20 or less, and further preferably 0.18 or less.
  • the average surface friction coefficient is an index indicating the texture of the synthetic leather (for example, smooth feeling, roughness), and the smaller the value, the smoother the surface. When the average surface friction coefficient is 0.25 or less, the smoothness of the synthetic leather for automobile interior materials becomes more excellent.
  • the lower limit of the average surface friction coefficient is not particularly limited, but is usually 0.10.
  • the basis weight of the synthetic leather for automobile interior materials is preferably 250 g / m 2 or more, more preferably 300 g / m 2 or more, still more preferably 350 g / m 2 or more, and preferably 550 g / m 2 or less, more preferably. It is 500 g / m 2 or less, more preferably 450 g / m 2 or less.
  • the synthetic leather is excellent in mechanical characteristics and lightweight for automobile interior materials.
  • Base Material As a fiber constituting the base layer of the nonwoven fabric or knitted fabric having a single layer or multilayer structure, a synthetic fiber made of a thermoplastic resin is preferable. Further, as a constituent fiber, natural fiber, regenerated fiber, semi-synthetic fiber, inorganic fiber, or the like may be mixed or mixed as necessary.
  • thermoplastic resin forming the synthetic fiber is not particularly limited as long as it has fiber-forming ability.
  • polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, and the main components thereof, and further isophthalic acid is used.
  • Polyesters such as low melting point polyesters used as copolymerization components; polypropylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, binary or ternary copolymer of propylene and other ⁇ -olefins
  • Polyolefins such as polymers; polyamides such as polyamide 6 and polyamide 66; or a mixture or copolymer thereof can be used.
  • Synthetic fibers obtained from such thermoplastic resins may be multicomponent systems such as a core-sheath type, an eccentric core-sheath type, a parallel type, and a sea-island type in addition to those of a single component type, and the shape of the fiber cross section There are no particular restrictions.
  • the synthetic fiber may contain various additives such as a matting agent, a pigment, an antioxidant, an ultraviolet absorber, a light stabilizer, a crystal nucleating agent, a flame retardant, and an acaricide as necessary. .
  • the basis weight of the base material layer is preferably 50 g / m 2 or more, more preferably 100 g / m 2 or more, still more preferably 150 g / m 2 or more, preferably 350 g / m 2 or less, more preferably 400 g / m 2. m 2 or less, more preferably 450 g / m 2 or less.
  • a lightweight synthetic leather for automobile interior materials is obtained that is excellent in mechanical properties.
  • a nonwoven fabric having a two-layer structure in which a fiber structure constituting an upper layer and a fiber structure constituting a lower layer are laminated by mechanical entanglement is preferable.
  • the basis weight of the upper layer is 40 g / m 2 or more and 150 g / m 2 or less
  • the fineness of the fibers constituting the upper layer is 0.0001 dtex or more and 0.5 dtex or less
  • the basis weight of the lower layer is 40 g / m 2 or more and 200 g / m. 2 or less
  • a nonwoven fabric having a two-layer structure fineness of the fiber constituting the lower layer is less than 10.0dtex than 1.5dtex are preferred.
  • the raw nonwoven fabric used for the base material layer may be either a short fiber nonwoven fabric or a long fiber nonwoven fabric for both the upper layer and the lower layer, but a long fiber nonwoven fabric is preferable from the viewpoint of ensuring better mechanical properties.
  • the manufacturing method is not particularly limited, preferred methods include a spunbond method and a melt blow method for a long-fiber nonwoven fabric, and a carding method and an airlay method for a short-fiber nonwoven fabric.
  • the fineness of the fibers constituting the upper layer base material of the raw material nonwoven fabric By setting the fineness of the fibers constituting the upper layer base material of the raw material nonwoven fabric to be the base material layer to 0.5 dtex or less, the denseness is high, there is almost no erection, the texture preferred by consumers, and excellent flexibility It becomes a base material.
  • the minimum of the fineness of the fiber which comprises an upper layer base material is not specifically limited, It is preferable from a viewpoint of maintaining intensity
  • the fineness of the fibers constituting the upper layer base material is more preferably 0.01 dtex or more, further preferably 0.1 dtex or more, more preferably 0.4 dtex or less, and still more preferably 0. .3 dtex or less.
  • the nonwoven fabric constituting the upper layer lacks a solid feeling and luxury, and lacks basic mechanical performance such as strength as an interior material for automobiles. Therefore, as a lower layer, a non-woven fabric having a fiber fineness of 1.5 dtex or more and 10.0 dtex or less is laminated and integrated so that it has excellent mechanical properties, is flexible, lightweight, has very little boneiness, has a profound feeling, and a high-class feeling. A certain leather for automobile interior materials is obtained. When the fineness of the fibers constituting the lower layer base material is 1.5 dtex or more and 10.0 dtex or less, a base material having both bulkiness and flexibility can be obtained.
  • the fineness of the fibers constituting the lower layer substrate is more preferably 1.5 dtex or more, further preferably 2.0 dtex or more, more preferably 8.0 dtex or less, and still more preferably. It is 6.0 dtex or less.
  • Basis weight of the upper substrate 40 g / m 2 or more, more preferably 50 g / m 2 or more, more preferably 60 g / m 2 or more, preferably 150 g / m 2 or less, more preferably 140 g / m 2 or less, more preferably 120 g / m 2 or less. If the basis weight of the upper layer base material is 40 g / m 2 or more, the anti-settling effect by densification is exhibited extremely effectively, and if it is 150 g / m 2 or less, needle punch or water punch with the lower layer base material, etc. The mechanical entanglement is effectively done.
  • Basis weight of the lower layer substrate 40 g / m 2 or more, more preferably 50 g / m 2 or more, still more preferably 60 g / m 2 or more, preferably 200 g / m 2 or less, more preferably 180 g / m 2 or less, more preferably 160 g / m 2 or less. If the basis weight of the lower layer base material is 40 g / m 2 or more, a heavy feeling and high-class feeling of the base material can be obtained, and if it is 200 g / m 2 or less, the excellent anti-settling property due to densification of the upper layer is inhibited. Thus, a substrate having an excellent texture and a heavy thickness can be obtained.
  • the initial stress of the lower layer base material is 0.1 N / 5 cm or more and 40 N / 5 cm or less in both warp and weft.
  • the initial stress of the lower layer base material is in the above-mentioned range, combined with the flexibility of the upper layer, strong entanglement is obtained between the upper and lower layers, and a highly integrated laminated base material is obtained.
  • the initial stress of the lower layer is more preferably 1 N / 5 cm or more, further preferably 3 N / 5 cm or more, and more preferably 20 N / 5 cm or less. More preferably, it is 10 N / 5 cm or less.
  • the density of the groups lower layer are laminated material, preferably 120 kg / m 3 or more, more preferably 130 kg / m 3 or more, still more preferably 140 kg / m 3 or more, preferably 250 kg / m 3 or less, More preferably, it is 240 kg / m 3 or less, and further preferably 230 kg / m 3 or less. If the density of the base material is 120 kg / m 3 or more, the denseness is improved and the occurrence of erection can be further suppressed. Moreover, if the density of a base material is 250 kg / m ⁇ 3 > or less, thickness will not fall too much and a heavy feeling and a high-class feeling will become favorable.
  • the burst strength of the base material on which the upper layer and the lower layer are laminated is preferably 400N or more and 1000N or less, more preferably 500N or more and 900N or less. If it is 400 N or more, for example, even if it is used as a seat skin material for an automobile interior material after being processed into a synthetic leather, the problem of tearing at the time of expansion hardly occurs, and the application range is expanded.
  • the bending resistance of the base material on which the upper layer and the lower layer are laminated is preferably 1 mm or more and 120 mm or less, more preferably 50 mm or more and 120 mm or less, and further preferably 70 mm or more and 100 mm or less. This is because if it has a flexibility of 1 mm or more and 120 mm or less, it will be finished into a final product utilizing the flexibility of the base material even when processed as a synthetic leather for automobile interior materials.
  • Synthetic resin examples of the synthetic resin forming the resin layer include polyurethane resin, polyamide resin, polyacrylate resin, vinyl acetate resin, and polyacrylonitrile resin. These synthetic resins may be used alone or in combination of two or more. Among these, a polyurethane resin is preferable.
  • the constituent component of the polyurethane resin generally include a polyurethane resin and a polyurethane urea resin. These are obtained by reacting a polyol such as a polyalkylene ether glycol having a molecular weight of 400 to 4000, a polyester polyol having a hydroxyl group at a terminal, a poly ⁇ -caprolactone polyol or a polycarbonate polyol, alone or as a mixture, with an organic diisocyanate. If necessary, the chain may be extended with a compound having two active hydrogens.
  • a polyol such as a polyalkylene ether glycol having a molecular weight of 400 to 4000
  • a polyester polyol having a hydroxyl group at a terminal a poly ⁇ -caprolactone polyol or a polycarbonate polyol
  • the chain may be extended with a compound having two active hydrogens.
  • polyalkylene ether glycol examples include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol, glycerin propylene oxide adduct, polyether polyol having ethylene oxide added to the terminal, and vinyl monomer grafted polyether polyol.
  • polyester polyol examples include alkylene glycols such as ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, and neopentyl glycol, and succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, and fumaric acid.
  • Carboxylic acid such as phthalic acid and trimellitic acid, and the like which are obtained by reacting with hydroxyl acid at the end.
  • Examples of the polycarbonate polyol include polyethylene carbonate diol, polytetramethylene carbonate diol, and polyhexamethylene carbonate diol. These may be used alone or in combination of two or more.
  • organic diisocyanates examples include aromatic isocyanates such as 2,4- and 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, and xylylene diisocyanate; 1,6-hexamethylene And aliphatic isocyanates such as diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 3-isocyanate methyl-3,5,5′-trimethylcyclohexyl isocyanate, and 2,6-diisocyanate methyl caproate. These may be used alone or in combination of two or more.
  • chain extender examples include diamines such as hydrazine, ethylenediamine, tetramethylenediamine, piperazine, and isophoronediamine; ethylene glycol, butylene glycol, hexylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, dimethylolpropionic acid, Glycols that can improve hydrophilicity such as ethylene oxide adducts to aminoethanesulfonic acid can be used alone or in combination.
  • diamines such as hydrazine, ethylenediamine, tetramethylenediamine, piperazine, and isophoronediamine
  • ethylene glycol, butylene glycol, hexylene glycol diethylene glycol, dipropylene glycol, neopentyl glycol, dimethylolpropionic acid
  • Glycols that can improve hydrophilicity such as ethylene oxide adducts to aminoethanesulfonic acid
  • the polyurethane resin is preferably a polycarbonate-based polyurethane resin using a polycarbonate polyol as a constituent component because of its excellent hydrolysis resistance.
  • a silicone-modified polycarbonate polyurethane resin in order to improve the texture of the synthetic leather.
  • the silicone-modified polycarbonate-based polyurethane has an organopolysiloxane skeleton in the molecular chain, or is sealed with a functional group that is non-reactive with an isocyanate group at the molecular chain end, for example, a trialkylsilyl group or a triarylsilyl group.
  • Hygroscopic fine particles are fine particles having hygroscopicity, as the name suggests.
  • Preferable examples of such fine particles include those obtained using an acrylic cross-linked polymer as a raw material.
  • it is preferable that 50% by mass or more (preferably 70% by mass or more, more preferably 90% by mass or more) of the hygroscopic fine particles is obtained from an acrylic crosslinked polymer as a raw material. It is preferable that it consists only of what used the acrylic type crosslinked polymer as a raw material.
  • This “acrylic crosslinked polymer” refers to (meth) acrylic acid; (meth) acrylic acid ester such as methyl (meth) acrylate and ethyl (meth) acrylate; acrylic acid such as (meth) acrylic amide; A copolymer monomer composition in which other copolymer monomers are added to an acrylonitrile monomer having at least a polymerizable vinyl group and a nitrile group such as (meth) acrylonitrile, if necessary, is copolymerized It means what introduce
  • the acrylic monomer or acrylonitrile monomer used in the above acrylic polymer may be used alone or in combination of two or more.
  • the other comonomer is not particularly limited as long as it does not impair the action of the finally obtained hygroscopic fine particles.
  • vinyl halide, vinylidene halide, p-styrenesulfonate And the like, and sulfonic acid-containing monomers and salts thereof, vinyl compounds such as styrene and vinyl acetate, vinylidene compounds, and the like can be used.
  • a method of adding a compound having two or more polymerizable vinyl groups as a copolymerization component for forming a crosslinked structure to the above copolymerizable monomer composition and copolymerizing the compound can be employed.
  • the compound having two or more polymerizable vinyl groups triallyl isocyanurate, triallyl cyanurate, divinylbenzene, ethylene glycol di (meth) acrylate, methylenebisacrylamide and the like are preferably used.
  • the acrylic polymer is an acrylonitrile polymer obtained by copolymerizing a copolymer monomer composition in which another copolymer monomer is added to an acrylonitrile monomer as required, It is also possible to introduce a crosslinked structure by treatment with a hydrazine compound.
  • hydrazine compounds that can be used in this case include hydrazine; hydrated hydrazine, sulfate hydrazine, hydrazine hydrochloride, hydrazine nitrate, hydrazine bromate, hydrazine carbonate, and the like; ethylenediamine, sulfate guanidine, guanidine hydrochloride, guanidine nitrate, phosphate And hydrazine derivatives such as guanidine and melamine.
  • Each of the above acrylic cross-linked polymers has a carboxyl group or a functional group that can be modified to a carboxyl group, and the carboxyl group or a functional group that can be modified to a carboxyl group is chemically converted to a salt-type carboxyl group. By causing it to absorb, hygroscopic fine particles are obtained.
  • hygroscopic fine particles include, for example, an acrylonitrile-based crosslinked polymer in which a crosslinked structure is introduced by a hydrazine-based compound into an acrylonitrile-based polymer obtained by copolymerizing a comonomer composition containing 50% by mass or more of acrylonitrile, Alternatively, these polymers are used for the acrylonitrile-based crosslinked polymer obtained by copolymerizing a comonomer composition containing 50% by mass or more of acrylonitrile and further containing a compound having two or more polymerizable vinyl groups. Examples thereof include those obtained by chemically converting a nitrile group therein to a salt-type carboxyl group by hydrolysis and containing 1.0 mmol / g or more of the salt-type carboxyl group.
  • an acrylonitrile polymer obtained by copolymerizing a comonomer composition containing 85% by mass or more of acrylonitrile has an increase in nitrogen content of 0.1 to 15.0% by mass.
  • the remaining nitrile group of the acrylonitrile-based crosslinked polymer introduced with a crosslinked structure by treatment with a hydrazine compound is chemically converted to a salt-type carboxyl group by hydrolysis, and the salt-type carboxyl group is converted to 1
  • a comonomer composition containing 0.0 mmol / g or more of hygroscopic fine particles (B) 50% by mass or more of acrylonitrile, and further containing divinylbenzene or triallyl isocyanurate and other comonomer.
  • “increase in nitrogen content” means that the nitrogen content (% by mass) in the acrylonitrile polymer used as a raw material and a crosslinked structure introduced into the resin by treatment with a hydrazine compound. It means the difference in the nitrogen content (mass%) after.
  • the nitrogen content is below the above range, the organic fine particles are dissolved in the hydrolysis step, and a salt-type carboxyl group cannot be introduced.
  • 1.0 mmol / g or more of the nitrile group cannot be converted into a salt-type carboxyl group.
  • the method for introducing a crosslinking with a hydrazine compound to an acrylonitrile-based polymer is not particularly limited as long as the increase in the nitrogen content by the crosslinking is 0.1 to 15.0% by mass, but the hydrazine compound is not limited. Means for treatment at a concentration of 1 to 80% by mass and a temperature of 50 to 120 ° C. for 0.2 to 10 hours are industrially preferable.
  • the hygroscopic fine particles in addition to the above-mentioned acrylonitrile-based cross-linked polymer as a raw material, it contains 5% by mass or more of an acrylate ester, and further contains divinylbenzene or triallyl isocyanurate, and other comonomer.
  • a methyl ester part of an acrylic ester cross-linked polymer obtained by copolymerizing a comonomer composition and introducing a cross-linked structure is chemically converted into a salt-type carboxyl group by hydrolysis, and the salt-type carboxyl Hygroscopic fine particles containing 1.0 mmol / g or more of groups can also be preferably used.
  • the particle diameter of the hygroscopic fine particles is not particularly limited as long as it does not impair the mechanical properties of the synthetic leather for automobile interior materials, and can be appropriately selected depending on the application. However, since the surface roughness may not be preferred by consumers when used on a handle or sheet skin material that is directly touched by a person, the average particle size is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, More preferably, it is 20 ⁇ m or less.
  • the lower limit of the average particle size of the hygroscopic fine particles is not particularly limited, but 1 ⁇ m or more is preferable.
  • the content of hygroscopic fine particles in the resin layer of the synthetic leather for automobile interior materials is preferably 2 g / m 2 or more, more preferably 5 g / m 2 or more.
  • the content is not particularly limited, but is preferably 50 g / m 2 or less, more preferably 30 g / m 2 or less, and even more preferably 20 g in consideration of the finish of synthetic leather, cost performance, and the like. / M 2 or less.
  • the outermost layer preferably contains hygroscopic fine particles.
  • the content of the hygroscopic fine particles in the outermost layer is preferably 2 g / m 2 or more, more preferably 5 g / m 2 or more, preferably 40 g / m 2 or less, more preferably 20 g / m 2. 2 or less.
  • the synthetic leather for automobile interior materials of the present invention can be produced by forming a resin layer on a base material layer.
  • the method of forming the resin layer is not particularly limited, and a method of forming a resin layer by applying a liquefied synthetic resin with a solvent and then drying the solvent, and forming by reacting the resin after applying a liquid resin
  • a dry method such as a method for laminating; a laminating method for attaching a resin film made of a synthetic resin; a wet method for applying a liquid resin to a coagulation bath and coagulating it.
  • the surface of the synthetic leather can be embossed or textured as necessary to obtain a desired appearance.
  • a polyurethane-based adhesive as an adhesive used for attaching the resin film in consideration of an adhesive force with the skin layer.
  • the polyurethane-based adhesive include polyether-based, polyester-based, polycarbonate-based, or a composite type thereof.
  • the adhesive preferably has a 100% modulus of the cured product of 0.5 MPa or more and 5 MPa or less, and is preferably 0.5 MPa or more and 3 MPa or less in consideration of bending resistance.
  • the synthetic leather for automobile interior materials according to the present invention is a synthetic leather, has a low ⁇ H (increase value of palm humidity), is excellent in moisture absorption characteristics, and has a smooth feel without stickiness. . Therefore, taking advantage of the above characteristics, it is useful for automobile interior materials, particularly steering skins, console BOX skins, shift cover materials, instrument panel materials, door trim materials, ceiling skin materials, car seat skin materials, and the like. Of course, it can also be used in combination with other materials that should meet the required performance in relation to the application, and can be processed and given a shape within a range that does not degrade the performance of the present invention. Furthermore, it is also possible to impart functions such as flame retardancy, insecticidal antibacterial properties, heat resistance, water and oil repellency, coloring, and aromaticity by adding chemicals at any stage of commercialization.
  • the sweating simulation device includes a heat producing sweating mechanism comprising a heat plate having a sweating hole and a heat producing body, a water supply mechanism for supplying water to the sweating hole, a heat producing control mechanism for controlling the temperature of the heat producing body, It consists of a humidity sensor.
  • the base of the hot plate is made of brass, has an area of 120 cm 2 , is provided with six sweat holes, and is controlled at a constant temperature by a heat-producing body composed of a planar heater.
  • the water supply mechanism uses a tube pump, and sends out a constant amount of water to the sweat holes of the substrate.
  • the hot plate is made by attaching simulated skin made of polyester multifilament woven fabric with a thickness of 0.1 mm to the surface of the substrate, which spreads the water discharged from the sweat holes to the surface of the substrate and creates a sweating state. It is.
  • An outer frame having a height of 0.5 cm is provided around the substrate, and the sample can be set at a position 0.5 cm away from the substrate.
  • the temperature / humidity sensor is installed in a space between the hot plate and the sample (synthetic leather), and measures the humidity of the “space surrounded by the substrate, the sample and the outer frame” when the substrate is in a sweat state.
  • the average surface friction coefficient (MIU) was measured using a surface friction coefficient measuring instrument (KES-SE) manufactured by Kato Tech Co., Ltd.
  • the measurement conditions were a standard friction element (fingerprint type), a load at friction of 1.47 N / cm 2 (150 gf / cm 2 ), and a measurement sensitivity L (high sensitivity 100 g / V).
  • Other conditions such as the friction distance and the friction speed are as specified in the apparatus specifications (friction distance 30 mm, analysis distance 20 mm, sample moving speed 1 mm / sec).
  • Average particle size Using a laser diffraction particle size distribution analyzer “SALD-200V” manufactured by Shimadzu Corporation, water was measured as a dispersion medium, and the average particle size was determined from the particle size distribution expressed on a volume basis.
  • Amount of salt-type carboxyl group 1 g of a sufficiently dried sample is precisely weighed (X (g)), 200 ml of water is added thereto, and then a 1 mol / l aqueous hydrochloric acid solution is added while heating to 50 ° C. to adjust the pH to 2.
  • X (g) 200 ml of water is added thereto, and then a 1 mol / l aqueous hydrochloric acid solution is added while heating to 50 ° C. to adjust the pH to 2.
  • all the carboxyl groups contained in the sample were H-type carboxyl groups.
  • a titration curve was obtained according to a conventional method using a 0.1 mol / l NaOH aqueous solution.
  • Density of non-woven fabric It was converted into a weight per 1 m 3 from the basis weight and thickness determined according to JIS-L 1913 (2010), and the density was defined as g / m 3 . Specifically, the thickness was measured by a thickness measuring instrument with a load of 2 kPa, and the density was determined by dividing the basis weight by the thickness.
  • Initial stress of nonwoven fabric was defined as stress at 5% elongation in tensile strength measured according to JIS-L 1913 (2010). Specifically, five test pieces having a width of 5 cm and a length of 30 cm were prepared, and a tensile test was performed on each of them to obtain an average value. The tensile test was performed by attaching to a constant speed extension type tensile tester with a grip interval of 20 cm, and applying a load until the test piece was cut at a tensile speed of 10 cm / min.
  • Nonwoven fabric (base material of Production Example 1 and Comparative Example 1)
  • an unbroken short fiber composite split nonwoven fabric with a basis weight of 80 g / m 2 which is a hollow petal split fiber composite fiber having a split fiber size of 0.24 dtex composed of polyamide 6 and polyethylene terephthalate, is prepared.
  • a filament group in which a polybutylene terephthalate resin (hereinafter abbreviated as “PBT”) is stretched by adjusting the air source pressure to a fineness of 2.0 dtex by a known spunbond method has a basis weight of 100 g.
  • PBT polybutylene terephthalate resin
  • the composite nonwoven fabric was obtained by carrying out the fiber entanglement of the upper layer division
  • the upper layer base material and the lower layer base material are then subjected to a high water pressure treatment by water punch, and the split fiber can be divided and laminated, and the upper layer and the lower layer can be entangled without peeling.
  • a laminated nonwoven fabric was obtained.
  • the density of the obtained laminated nonwoven fabric was 172 kg / m 3
  • the burst strength was 760 N
  • the bending resistance was 110 mm in the vertical direction and 81 mm in the horizontal direction.
  • Knitted fabric (base materials of Production Examples 2 to 8 and Comparative Examples 2 to 8) Using a polyester filament of 84 dtex / 36f, a tricot knitted fabric with a basis weight of 300 g / m 2 was obtained.
  • Fine particles 3-1 Hygroscopic fine particles No. 1 (average particle size; 3 ⁇ m) After 450 parts of acrylonitrile, 50 parts of methyl acrylate and 1181 parts of water were charged into a 2 liter autoclave, di-tert-butyl peroxide as a polymerization initiator was added in an amount of 0.5% based on the total amount of monomers. Sealed and then polymerized for 30 minutes at 120 ° C. under stirring. After completion of the reaction, the mixture was cooled to 90 ° C. while continuing stirring to obtain polymer particles having an average particle size of 2 ⁇ m.
  • Hygroscopic fine particles No. 2 (average particle size; 30 ⁇ m) A monomer mixture consisting of 55 parts of acrylonitrile, 10 parts of methyl acrylate, and 35 parts of divinylbenzene is added to 300 parts of an aqueous solution containing 0.5 part of ammonium persulfate, and then 0.6 part of sodium pyrosulfite is added, followed by polymerization with a stirrer. Polymerization was carried out in a tank at 65 ° C. for 2 hours. 15 parts of the obtained particles are dispersed in 85 parts of water, 10 parts of sodium hydroxide is added thereto, and a hydrolysis reaction is performed at 90 ° C. for 2 hours, followed by washing, dehydration and drying, and acrylic crosslinking. Polymer fine particles were obtained. The average particle diameter of the particles was 30 ⁇ m, and the amount of salt-type carboxyl groups was 6.3 mmol / g.
  • PMMA particle no. 1 (average particle size; 3 ⁇ m) Monomer by mixing 90 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 10 parts of polyvinyl alcohol and 300 parts of water and stirring with a homomixer. A dispersion was prepared and polymerized at 50 ° C. for 2 hours. The obtained particles were washed with water, dehydrated, dried, and then classified to obtain polymethyl methacrylate-based fine particles having an average particle diameter of 3 ⁇ m.
  • PMMA particle no. 2 (average particle size; 30 ⁇ m) Monomer by mixing 90 parts of methyl methacrylate, 10 parts of ethylene glycol dimethacrylate, 1 part of 2,2′-azobis (2,4-dimethylvaleronitrile), 10 parts of polyvinyl alcohol and 300 parts of water and stirring with a homomixer. A dispersion was prepared and polymerized at 50 ° C. for 2 hours. The obtained particles were washed with water, dehydrated, dried, and then classified to obtain polymethyl methacrylate-based fine particles having an average particle diameter of 30 ⁇ m.
  • Synthetic resin 4-1 Urethane resin
  • non-yellowing polycarbonate type polyurethane having a 100% modulus of 2 MPa or more and 10 MPa or less was used.
  • High slip urethane resin As the high slip urethane resin, a silicone-modified non-yellowing polycarbonate polyurethane having a 100% modulus of 5 MPa to 10 MPa was used.
  • the total weight of wet synthetic leather was 400 g / m 2 and the thickness was 1.3 mm. Further, apply a urethane resin dissolved in a solvent on the release paper with a comma coater to 25 g / m 2, and dry the film to be a dry layer, and apply an adhesive (about 30 g / m 2 ).
  • the wet synthetic leather was laminated, and then an aging treatment was performed to laminate a resin layer.
  • the total weight of the base material and the resin layer was 455 g / m 2 and the thickness was 1.6 mm.
  • a polyurethane adhesive was used as the adhesive.
  • the highly lubricious urethane resin has hygroscopic fine particles No. 1 was mixed, and a prescribed amount was applied by gravure coating on the resin layer formed above to form an outermost layer.
  • Synthetic leather was obtained by applying a genuine leather-like texture using release paper.
  • Production Examples 3-5 Synthetic leather was obtained in the same manner as in Production Example 2 except that the content of the hygroscopic fine particles to be mixed with the highly lubricious urethane resin, or the content and the average particle size were changed.
  • Hygroscopic fine particles No. in urethane resin dissolved in solvent. 1 was mixed and applied onto a release paper with a comma coater so as to be 25 g / m 2, and the film produced by drying was bonded to the knitted fabric coated with an adhesive (about 30 g / m 2 ), and then An aging treatment was performed to form a resin layer.
  • the total weight of the base material and the resin layer was 355 g / m 2 and the thickness was 0.9 mm.
  • the highly lubricious urethane resin has hygroscopic fine particles No. 1 was mixed, and a prescribed amount was applied by gravure coating on the resin layer formed above to form an outermost layer. Synthetic leather was obtained by applying a genuine leather-like texture using release paper.
  • Production Example 7 Hygroscopic fine particles No. in urethane resin dissolved in solvent. 1 was mixed and applied onto a release paper with a comma coater so as to be 25 g / m 2, and the film produced by drying was bonded to the knitted fabric coated with an adhesive (about 30 g / m 2 ), and then Aging treatment was performed to form a resin layer (outermost layer) to obtain a synthetic leather. That is, a synthetic leather was obtained in the same manner as in Production Example 6 except that the outermost layer was not formed with a highly slippery urethane resin.
  • Production Example 8 The fine particles mixed with the urethane resin are designated as PMMA particles No.
  • a synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
  • Production Example 9 Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 1 except that it was changed to 1.
  • Production Example 10 Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 2 except that the number was changed to 1.
  • Production Example 11 Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No.
  • a synthetic leather was obtained in the same manner as in Production Example 2 except that the content was changed to 1.
  • Production Example 12 Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No.
  • the synthetic leather was obtained in the same manner as in Production Example 2 except that the content was changed to 2.
  • Production Example 13 A synthetic leather was obtained in the same manner as in Production Example 7 except that the urethane resin was not mixed with fine particles.
  • Production Example 14 The fine particles mixed with the urethane resin and the fine particles mixed with the highly slippery urethane resin are both PMMA particles No. A synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
  • Production Example 15 The fine particles mixed with the urethane resin are designated as PMMA particles No.
  • a synthetic leather was obtained in the same manner as in Production Example 7 except that the number was changed to 1.
  • Production Example 16 Fine particles mixed with the highly lubricious urethane resin are designated as PMMA particles No.
  • a synthetic leather was obtained in the same manner as in Production Example 6 except that it was changed to 1.
  • Table 1 shows the composition of the synthetic leather obtained in Production Examples 1 to 16 and the evaluation results of the palm humidity and the average surface friction coefficient.
  • FIG. 1 shows the relationship between the average surface friction coefficient of the synthetic leather obtained in Production Examples 1 to 16 and the increase ( ⁇ H) in the palm humidity one minute after the start of sweating.
  • Reference Example 1 the same evaluation was performed on the genuine leather for car seats mounted on an actual vehicle, and the results are shown in FIG.
  • Table 2 shows the subjective evaluation results of the stickiness, smoothness, and roughness of the monitor.
  • a sticky sensation indicates that a positive score is not sticky
  • a smooth sensation is a positive score that feels smooth
  • a rough sensation indicates that a positive score is not rough.
  • the resin layer is multi-layered, and the content of hygroscopic fine particles in the outermost layer is larger than in other production examples, and it is presumed that the hygroscopic performance is excellent.
  • hygroscopic fine particles are contained in both the urethane resin layer and the highly slipping urethane resin layer, and it is assumed that the hygroscopic property is excellent. Therefore, in these production examples 2 and 6, the increase in the palm humidity is suppressed as compared with the genuine leather of Reference Example 1, and the samples are finished to be less sticky.
  • Production Example 3 is effective when the appearance and cost performance other than stickiness, smoothness, and roughness are taken into consideration.
  • the increase in the palmar humidity after 1 minute was 20% RH or less, and there was no stickiness and a smooth feel was obtained.
  • the production examples 1 to 8 were obtained.
  • Synthetic leather can be said to be a synthetic leather for automobile interior materials that has little stickiness and a smooth feel.
  • the synthetic leathers obtained in Production Examples 9 to 16 are all synthetic leathers for automobile interior materials in which the increase in palm humidity after 1 minute exceeds 20% RH and the stickiness is poor. It can be said.
  • the synthetic leather of the present invention uses a small amount of hygroscopic fine particles and uses a small amount of resin for imparting fine particles, and therefore has an effect of reducing the weight and is excellent in cost performance compared to conventional synthetic leather. It can be said that it is a synthetic leather for interior materials.
  • the synthetic leather for automotive interior materials of the present invention is useful for automotive interior materials, particularly steering skins, console BOX skins, shift cover materials, instrument panel materials, door trim materials, ceiling skin materials, car seat skin materials, and the like.
PCT/JP2010/071894 2010-12-07 2010-12-07 自動車内装材用合成皮革 WO2012077180A1 (ja)

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JP2014145133A (ja) * 2013-01-25 2014-08-14 Toyobo Co Ltd 合成皮革
WO2020045184A1 (ja) * 2018-08-30 2020-03-05 日本エクスラン工業株式会社 多孔質セラミックフィルタ製造用造孔材

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JP7144407B2 (ja) * 2017-05-19 2022-09-29 日本バイリーン株式会社 内装用表面材
CN111501363A (zh) * 2020-05-12 2020-08-07 明新孟诺卡(江苏)新材料有限公司 一种高仿真超纤制备方法

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