WO2023105285A1 - 表皮材料 - Google Patents

表皮材料 Download PDF

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Publication number
WO2023105285A1
WO2023105285A1 PCT/IB2022/000707 IB2022000707W WO2023105285A1 WO 2023105285 A1 WO2023105285 A1 WO 2023105285A1 IB 2022000707 W IB2022000707 W IB 2022000707W WO 2023105285 A1 WO2023105285 A1 WO 2023105285A1
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WO
WIPO (PCT)
Prior art keywords
skin material
resin
layer
topcoat layer
diisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/IB2022/000707
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
元彦 黒田
萌映 山▲崎▼
享介 竹下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Renault SAS
Seiren Co Ltd
Nissan Motor Co Ltd
Original Assignee
Renault SAS
Seiren Co Ltd
Nissan Motor Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Renault SAS, Seiren Co Ltd, Nissan Motor Co Ltd filed Critical Renault SAS
Priority to US18/717,621 priority Critical patent/US20250050627A1/en
Priority to EP22903648.8A priority patent/EP4446112A4/en
Priority to CN202280080418.0A priority patent/CN118354903A/zh
Priority to JP2023565651A priority patent/JPWO2023105285A1/ja
Publication of WO2023105285A1 publication Critical patent/WO2023105285A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0088—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by directly applying the resin
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—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 characterised by the macromolecular diols used
    • 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
    • D06N2209/10—Properties of the materials having mechanical properties
    • D06N2209/106—Roughness, anti-slip, abrasiveness
    • 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 skin materials.
  • genuine leather or synthetic leather is used for the skin material used for automobile steering, seats, doors, instrument panels, assist grips and grips.
  • the skin material for synthetic leather for example, a skin material provided with a top coat layer on the surface is used. In such a skin material, it has been demanded to improve the tactile sensation.
  • the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a skin material with excellent tactile sensation.
  • the inventors have conducted intensive research in order to solve the above problems.
  • the above problems can be solved by controlling the surface roughness of the topcoat layer and the average spacing of the protrusions to predetermined values, and by allowing the topcoat layer to contain resin beads having a predetermined average particle diameter. and completed the present invention.
  • the present invention provides a skin material having at least a topcoat layer, wherein the arithmetic mean roughness Ra of the surface of the topcoat layer is 12 ⁇ m or less, the average interval S of the convex portions is 250 to 450 ⁇ m, and the top
  • the coat layer is a skin material containing resin beads having an average particle size of 5 to 20 ⁇ m.
  • FIG. 1 is a schematic cross-sectional view of a skin material according to one embodiment of the invention.
  • One aspect of the present invention is a skin material having at least a topcoat layer, wherein the surface of the topcoat layer has an arithmetic mean roughness Ra of 12 ⁇ m or less, and an average interval S of convex portions of 250 to 450 ⁇ m,
  • the top coat layer is a skin material containing resin beads having an average particle size of 5 to 20 ⁇ m. According to the present invention, a skin material having excellent tactile sensation can be obtained.
  • tactile sensation is also important as an element that constitutes texture.
  • Sensitive factors representing tactile sensations include rough, smooth, dry and wet sensations, hard and soft sensations, and hot and cold sensations defined by KES.
  • the feeling of roughness and smoothness is a sensibility factor that expresses the unevenness of the surface, and is a tactile sensation such as "smooth” or "rough (rugged)" felt when touched.
  • the feeling of dryness and humidity is a sensory factor that expresses the moistness and sliminess of the surface, and is a tactile sensation such as "moist” or “smooth” when touched.
  • the surface arithmetic average roughness (hereinafter also referred to as surface roughness) Ra of the topcoat layer is set to 12 ⁇ m or less, and the average interval S of the protrusions is set to 250 to 450 ⁇ m. becomes close to the distance between fingerprints, giving the best rough smoothness.
  • the frictional resistance can be increased without affecting the surface arithmetic mean roughness Ra. As a result, it is considered that both a rough and smooth feeling and a dry and wet feeling could be achieved, and a moist and comfortable touch that could not be expressed with conventional skin materials could be obtained.
  • the skin material of the present invention is not particularly limited as long as it has a surface having a predetermined surface roughness and an average distance between protrusions, and has a topcoat layer containing resin beads having a predetermined average particle diameter.
  • the topcoat layer is preferably formed directly on the surface of the substrate or via another layer.
  • the topcoat layer is formed on the substrate via the surface layer.
  • an adhesive layer is provided between the surface layer and the substrate.
  • the skin material according to one embodiment of the present invention may be provided with another layer such as a urethane resin layer on the surface of the substrate opposite to the topcoat layer.
  • FIG. 1 is a schematic cross-sectional view schematically showing a skin material according to one embodiment of the present invention.
  • the skin material 1 of this embodiment has an adhesive layer 3, a surface layer 4, and a topcoat layer 5 in this order on one surface of a substrate 2. As shown in FIG.
  • the topcoat layer 5 also contains resin beads 6 .
  • the main constituent elements of the skin material described above will be described below.
  • the skin material of the present invention is not limited to the form shown in FIG.
  • topcoat layer The topcoat layer is formed on the outermost side of the skin material.
  • the "outermost side” intends the side that is directly touched by the user.
  • the surface arithmetic mean roughness Ra of the topcoat layer is 12 ⁇ m or less. If it exceeds 12 ⁇ m, a smooth touch cannot be obtained.
  • the above Ra is preferably 11 ⁇ m or less from the viewpoint of obtaining a tactile sensation with less unevenness.
  • the above Ra is preferably 5 ⁇ m or more, more preferably 7 ⁇ m or more, from the viewpoint of more easily obtaining a reduction in unevenness in accordance with a reduction in Ra.
  • the thickness is more preferably 9 ⁇ m or more.
  • Ra can be determined by the method described in the examples below.
  • the average spacing S between the protrusions on the surface of the topcoat layer is 250 to 450 ⁇ m. If it is less than 250 ⁇ m or more than 450 ⁇ m, it is not possible to obtain a suitable rough and smooth feeling, and therefore, it is not comfortable to the touch.
  • the above S is 280 to 420 ⁇ m. Within the above range, the effects of the present invention can be obtained more remarkably.
  • S is the average value of the intervals between adjacent convex portions (local peaks), and can be obtained by the method described in the Examples below.
  • the method for controlling the arithmetic mean roughness Ra and the mean spacing S of the convex portions of the surface of the topcoat layer is not particularly limited. It can be done by using
  • the topcoat layer contains resin beads with an average particle size of 5 to 20 ⁇ m.
  • resin beads include, but are not particularly limited to, acrylic beads, urethane beads, nylon beads, and styrene beads. Among these, acrylic beads or urethane beads are preferably used, and urethane beads are more preferably used, from the viewpoint of imparting excellent tactile sensation. Further, when the topcoat layer contains a urethane resin as a binder resin, the use of urethane beads is preferable because the dispersibility of the resin beads can be improved and the coatability can be improved.
  • crosslinked resin beads may be used. Examples of crosslinked resin beads include crosslinked acrylic beads and crosslinked urethane beads.
  • the average particle size of the resin beads is less than 5 ⁇ m, the surface frictional resistance cannot be sufficiently increased, and a moist touch cannot be obtained. On the other hand, when it exceeds 20 ⁇ m, the surface roughness is affected, and the touch may become rough.
  • the average particle size of the resin beads is 7 ⁇ m or more, the effect of increasing the frictional force is higher, and the wet and dry feeling is excellent, which is preferable.
  • the thickness is 15 ⁇ m or less, it is preferable because the resin beads are less likely to come off due to wear while providing an excellent rough and smooth feeling.
  • an average particle diameter is a value measured by surface SEM observation.
  • the content of the resin beads in the topcoat layer is not particularly limited, it is preferably 5 to 10% by mass (in terms of solid content) relative to the total amount of the topcoat layer.
  • the resin bead content is 5% by mass or more, the effect of increasing the surface frictional force is excellent.
  • the content is 10% by mass or less, the viscosity of the resin solution as the coating liquid does not become too high when the topcoat layer is produced, so that the coating can be easily performed, which is preferable.
  • the topcoat layer preferably contains a binder resin such as polyurethane resin.
  • a binder resin such as polyurethane resin.
  • Polyurethane resins are not particularly limited, but include polycarbonate polyurethane resins, polyester polyurethane resins, polyether polyurethane resins, and the like, and these can be used alone or in combination of two or more. Among them, polycarbonate polyurethane resin is preferable because it is excellent in abrasion resistance and weather resistance.
  • the form of the polyurethane resin can be solvent-free, hot-melt, solvent-based, or water-based, and it can be used regardless of whether it is a one-component type or a two-component curing type, depending on the purpose and application. It can be selected as appropriate.
  • a polycarbonate polyurethane resin is a polyurethane resin having a polycarbonate skeleton in its main chain, and is synthesized by a urethane reaction between a polycarbonate diol and a diisocyanate.
  • the polycarbonate polyurethane resin may be either non-crosslinked or crosslinked polycarbonate polyurethane resin.
  • the polycarbonate diol is obtained, for example, by reacting at least one carbonate compound selected from the group consisting of alkylene carbonate, diaryl carbonate and dialkyl carbonate with a diol and/or polyether polyol.
  • alkylene carbonate examples include, but are not limited to, ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, and the like.
  • diaryl carbonates include, but are not limited to, diphenyl carbonate, phenyl-naphthyl carbonate, dinaphthyl carbonate, 4-methyldiphenyl carbonate, 4-ethyldiphenyl carbonate, 4-propyldiphenyl carbonate, 4,4'-dimethyl- diphenyl carbonate, 4,4'-diethyl-diphenyl carbonate, 4,4'-dipropyl-diphenyl carbonate and the like.
  • dialkyl carbonates include, but are not limited to, dimethyl carbonate, diethyl carbonate, di-n-propyl carbonate, diisopropyl carbonate, di-n-butyl carbonate, diisobutyl carbonate, di-t-butyl carbonate, di-n- amyl carbonate, diisoamyl carbonate and the like.
  • diols to be reacted with the carbonate compound include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2 -methyl-1,3-propanediol, neopentyl glycol, 2-methyl-pentanediol, 3-methyl-pentanediol, 2,2,4-trimethyl-1,6-hexanediol, 2,3,5-trimethyl pentanediols and mixtures thereof;
  • polyether polyols include, but are not limited to, polytetramethylene glycol obtained by ring-opening polymerization of tetrahydrofuran, alkylene oxide adducts of diols, and mixtures thereof.
  • diols examples include, but are not limited to, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, isomeric pentanediols , isomeric hexanediols or octanediols (e.g. 2-ethyl-1,3-hexanediol, 1,2-bis(hydroxymethyl)-cyclohexanone, 1,3-bis(hydroxymethyl)-cyclohexanone, 1 , 4-bis(hydroxymethyl)-cyclohexanone, trimethylolpropane), glycerin and the like.
  • ethylene glycol 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol
  • isomeric pentanediols isomeric
  • alkylene oxides include, but are not limited to, ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 2,3-butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, and the like. mentioned.
  • the above alkylene oxides may be used alone or in combination of two or more.
  • the above diols and polyether polyols may also be used alone or in combination of two or more.
  • diisocyanates include, but are not limited to, aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate (HDI); alicyclic diisocyanates such as 1,4-cyclohexane diisocyanate and isophorone diisocyanate (IPDI); aromatic diisocyanates such as diisocyanate (TDI), xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI); The above reaction may be carried out in the presence of a chain extender such as 1,4-butanediol, 1,6-hexanediol, ethylenediamine.
  • a chain extender such as 1,4-butanediol, 1,6-hexanediol, ethylenediamine.
  • the molecular weight (weight average molecular weight) of the polycarbonate polyurethane resin is not particularly limited, but is preferably from 15,000 to 150,000.
  • the above polycarbonate polyurethane resins may be used alone or in the form of a mixture of two or more.
  • a polyester polyurethane resin is a polyurethane resin that has a polyester skeleton in its main chain, and is synthesized by the reaction of polyester polyol and diisocyanate. In addition, the above reaction may be performed in the presence of a chain extender.
  • polyester polyols include, but are not limited to, dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, and terephthalic acid.
  • ethylene glycol propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, 1,8-octamethylenediol, neopentyl glycol, bishydroxymethylcyclohexane, bishydroxyethylbenzene, alkyl Examples thereof include those obtained by polycondensation with glycols such as dialkanolamine.
  • diisocyanates include, but are not limited to, 1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane diisocyanate, 4,4′-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4- trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate, isophorone diisocyanate, lysine di
  • a polyether polyurethane resin is a polyurethane resin that has a polyether skeleton in its main chain, and is synthesized by the reaction of polyether polyol and diisocyanate. In addition, the above reaction may be performed in the presence of a chain extender.
  • the polyether polyol is not particularly limited, but the same polyether polyol as described in the section of the polycarbonate polyurethane resin can be used.
  • diisocyanates include, but are not limited to, hexamethylene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, cyclohexane diisocyanate, toluidine diisocyanate, 2,4-tolylene diisocyanate Aliphatic diisocyanates such as isocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate and 1,5-naphthalene diisocyanate, and aromatic diisocyanates.
  • the above diisocyanates may be used alone or in combination of two or more.
  • the molecular weight (weight average molecular weight) of the polyether polyurethane resin is not particularly limited, it is preferably 15,000 to 150,000.
  • the above polyether polyurethane resins may be used alone or in the form of a mixture of two or more.
  • each resin in the topcoat layer can be confirmed by, for example, NMR measurement ( 1 H-NMR measurement, 13 C-NMR measurement, etc.), infrared spectrum analysis, GC-MS analysis, and the like.
  • the topcoat layer may contain other components in addition to the above components.
  • other components are not particularly limited, and known materials commonly used for topcoat layers of leather materials can be used in the same manner.
  • pigments e.g., isocyanate-based cross-linking agents, carbodiimide-based cross-linking agents), auxiliaries, tactile agents (e.g., silicone-based tactile agents), leveling agents, thickeners, UV absorbers. agents and the like.
  • cross-linking agent e.g., isocyanate-based cross-linking agents, carbodiimide-based cross-linking agents
  • auxiliaries e.g., isocyanate-based cross-linking agents, carbodiimide-based cross-linking agents
  • tactile agents e.g., silicone-based tactile agents
  • leveling agents thickeners
  • UV absorbers. agents and the like e.g., UV absorbers. agents and the like.
  • the cross-linking agent promotes cross-linking of the resins when
  • the dynamic friction coefficient ⁇ d of the topcoat layer is not particularly limited, but is, for example, 0.35 or more, preferably 0.40 to 0.60, more preferably 0.48 to 0.56, and 0 0.52 to 0.56 is even more preferable, and 0.54 to 0.56 is particularly preferable. Within the above range, a more excellent wet and dry feeling can be obtained.
  • the dynamic friction coefficient ⁇ d of the topcoat layer can be obtained by the method described in the following Examples.
  • the thickness (dry thickness) of the topcoat layer is not particularly limited, but is, for example, 1 to 200 ⁇ m, preferably 2 to 100 ⁇ m. When the thickness is 1 ⁇ m or more, the abrasion resistance of the obtained skin material can be improved. Further, if the thickness is 200 ⁇ m or less, the resulting skin material can have a good texture.
  • the substrate is not particularly limited, and polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, resin film substrates such as polyolefin resins such as polypropylene, and fibrous substrates can be used. , preferably fibrous substrates.
  • the fibrous base material is not particularly limited, and examples thereof include fabrics such as knitted fabrics, woven fabrics and non-woven fabrics, and natural leather (including split leather).
  • the fabric is coated or impregnated with conventionally known solvent-based or solvent-free (including water-based) polymer compounds (e.g., polyurethane resins, copolymers thereof, and polyvinyl chloride resins), followed by dry coagulation or wet coagulation.
  • the fabric may be provided with a known pretreatment agent (for example, penetrant, water repellent, flame retardant, ultraviolet absorber, etc.).
  • a known pretreatment agent for example, penetrant, water repellent, flame retardant, ultraviolet absorber, etc.
  • the fibrous base material may be colored with dyes or pigments. Furthermore, the surface of the fibrous base material may be raised by a conventionally known raising treatment.
  • the type of fibers constituting the fibrous base material is not particularly limited, and conventionally known fibers such as natural fibers, regenerated fibers, semi-synthetic fibers, and synthetic fibers can be mentioned, and two or more of these can be combined. may be Among them, synthetic fibers are preferred, and polyester fibers are more preferred, from the viewpoint of strength and workability.
  • the thickness of the base material is not particularly limited, and conventionally known knowledge can be appropriately employed, and can be, for example, 0.1 to 10 mm.
  • the density of the base material is also not particularly limited, but when using a fibrous base material, it can be, for example, 0.05 to 5 g/cm 3 .
  • a surface layer may be arranged on the substrate.
  • the surface layer may be provided directly on the substrate, or may be provided via another layer such as an adhesive layer.
  • the top coat layer can be stably formed on the surface layer. Further, as will be described later, by providing unevenness on the surface of the surface layer, desired surface roughness and unevenness can be imparted to the surface of the topcoat layer.
  • the surface layer is not particularly limited, and materials similar to those commonly used in the field of leather materials can be applied, but resins such as polyurethane resins are preferably included.
  • the polyurethane resin used for the surface layer is not particularly limited, and conventionally known polyurethane resins can be used. Examples thereof include polyether polyurethane resins, polyester polyurethane resins, polycarbonate polyurethane resins, and the like, and these can be used singly or in combination of two or more. Among them, polycarbonate polyurethane resin is preferable from the viewpoint of wear resistance, and polyether polyurethane resin is preferable from the viewpoint of texture.
  • polyurethane resin such as polyether polyurethane resin, polyester polyurethane resin, polycarbonate polyurethane resin, etc.
  • the form of the polyurethane resin may be hot-melt, solvent-based, water-based, etc., and may be one-component or two-component curing type, and may be selected appropriately according to the purpose and application. Just do it.
  • the surface layer may optionally contain known additives such as heat stabilizers, thermoplastic resins, thermosetting resins, pigments, flame retardants, conductivity imparting agents, antistatic agents, moisture permeability improvers, and water repellents. , an oil repellent, a water absorbent, a moisture absorbent, a deodorant, an antifoaming agent, a pigment dispersant, a hydrolysis inhibitor, a cross-linking agent, a thickener, and the like.
  • additives such as heat stabilizers, thermoplastic resins, thermosetting resins, pigments, flame retardants, conductivity imparting agents, antistatic agents, moisture permeability improvers, and water repellents.
  • an oil repellent a water absorbent, a moisture absorbent, a deodorant, an antifoaming agent, a pigment dispersant, a hydrolysis inhibitor, a cross-linking agent, a thickener, and the like.
  • the thickness of the surface layer is not particularly limited, it is, for example, 5 to 100 ⁇ m, preferably 20 to 50 ⁇ m. If the thickness is 5 ⁇ m or more, the abrasion resistance is excellent. Moreover, it is preferable that the thickness is 100 ⁇ m or less because the texture is excellent.
  • the base material and the surface layer may be laminated directly, or may be bonded together via an adhesive layer.
  • the presence of the adhesive layer is preferable because excessive penetration of the resin forming the surface layer into the base material is suppressed. In addition, the formation of non-uniform pores in the surface layer is suppressed, and the touch and feel of natural leather can be provided.
  • the material forming the adhesive layer is not particularly limited, but the same resin as that used for the surface layer can be used, and for example, polyurethane resin can be preferably used.
  • the thickness of the adhesive layer (dry thickness) is also not particularly limited, but is, for example, 1 to 500 ⁇ m.
  • the method for producing the skin material of this embodiment is not particularly limited.
  • a method can be used that includes the following steps: (1) a step of applying a surface layer resin solution onto a release substrate to form a surface layer; (2) a step of bonding the surface layer and the base material together; (3) a step of peeling off the releasable substrate; (4) A step of applying a resin solution for a top coat layer to the surface from which the release base material of the surface layer has been removed to form a top coat layer.
  • the resin solution for the surface layer can be obtained by mixing additives, solvents, etc. with the above-mentioned resin constituting the surface layer, if necessary.
  • a method for applying the resin solution for the surface layer onto the releasable base material conventionally known various methods can be employed, and the method is not particularly limited.
  • a method using an apparatus such as a reverse roll coater, spray coater, roll coater, knife coater and comma coater can be used.
  • a reverse roll coater, a roll coater, a spray coater, or a comma coater is preferable in that a uniform thin film layer can be formed.
  • the releasable base material is not particularly limited, and any base material having releasability to polyurethane resin or the like or a base material subjected to a releasable treatment may be used. Examples thereof include release paper, release-treated cloth, water-repellent treated cloth, olefin sheet or film made of polyethylene resin or polypropylene resin, fluororesin sheet or film, and plastic film with release paper.
  • the release substrate has unevenness, and the height of the unevenness (a value defined in the same manner as Ra above) The specified value) may be appropriately set so as to provide the top coat layer with the desired surface roughness Ra and the average interval S between the protrusions.
  • heat treatment is performed as necessary.
  • the heat treatment is performed to evaporate the solvent in the surface layer resin solution and dry the resin.
  • a cross-linking agent that causes a cross-linking reaction by heat treatment or when a two-component curing resin is used, the reaction is accelerated to form a film having sufficient strength.
  • the heat treatment temperature is not particularly limited, it is, for example, 50 to 150°C, preferably 60 to 140°C.
  • the heat treatment temperature is 50° C. or higher, the heat treatment does not take too much time, so the process load does not become too large.
  • the heat treatment temperature is 150° C. or lower, the texture of the skin material is excellent.
  • the heat treatment time is not particularly limited, but is, for example, 1 to 20 minutes, preferably 1 to 10 minutes. If the heat treatment time is 1 minute or more, insufficient cross-linking of the resin can be prevented, and thus poor wear resistance can be prevented.
  • the heat treatment time is within 20 minutes, the process load does not become too large.
  • the surface layer and the base material eg, fibrous base material
  • the adhesive layer may be interposed therebetween, or direct lamination may be performed.
  • the means for forming the adhesive layer is not particularly limited, but the resin constituting the adhesive layer is mixed with additives, solvents, etc. as necessary to prepare a resin solution for the adhesive layer, and this is applied to the surface layer or the base material. can be used.
  • Various known methods can be employed for applying the adhesive layer resin solution, and the method is not particularly limited. For example, a method using an apparatus such as a reverse roll coater, a spray coater, a roll coater, a gravure coater, a kiss roll coater, a knife coater and a comma coater can be used.
  • a topcoat layer having an uneven surface can be formed by applying a topcoat layer resin solution onto the surface layer.
  • the resin solution for the topcoat layer can be obtained, for example, by mixing resin beads, a binder resin constituting the topcoat layer, additives, other components, a solvent, and the like.
  • the method of applying the resin solution for the top coat layer is not particularly limited, and examples thereof include methods using devices such as reverse roll coaters, spray coaters, roll coaters, gravure coaters, kiss roll coaters, knife coaters, and comma coaters. can be mentioned.
  • the coating thickness may be appropriately set according to the desired thickness of the topcoat layer.
  • heat treatment is performed if necessary.
  • the heat treatment evaporates the solvent in the resin solution for the topcoat layer and dries the resin. and to form a film with sufficient strength.
  • the heat treatment temperature is preferably 50-150°C, more preferably 60-140°C.
  • the heat treatment temperature is 50° C. or higher, the heat treatment can be performed in a short time, and the process load is small.
  • the heat treatment temperature is 150° C. or lower, the texture of the skin material is excellent.
  • the heat treatment time is preferably 1 to 20 minutes, more preferably 1 to 10 minutes. If the heat treatment time is 1 minute or more, insufficient cross-linking of the resin can be prevented, and thus poor wear resistance can be prevented. When the heat treatment time is within 20 minutes, the process load does not become too large.
  • the skin material of the present invention has a moist feel like genuine leather. Therefore, the skin material of the present invention can be used for various products including automobile interior materials, interior products such as sofas, shoes, and bags. In particular, the skin material of the present invention can be suitably used for, for example, steering wheels, seats, doors, instrument panels, assist grips and grips for automobiles.
  • the present invention includes the following aspects and forms: 1. A skin material having at least a topcoat layer, The arithmetic average roughness Ra of the surface of the topcoat layer is 12 ⁇ m or less, and the average interval S of the convex portions is 250 to 450 ⁇ m, A skin material in which the topcoat layer contains resin beads having an average particle size of 5 to 20 ⁇ m; 2. 1. The top coat layer contains 5 to 10% by mass of the resin beads in terms of solid content with respect to the total amount of the top coat layer. The skin material according to; 3. 1. The resin beads have an average particle size of 7 to 15 ⁇ m. or 2. The skin material according to; 4. 1. The Ra is 9 to 11 ⁇ m. ⁇ 3. The skin material according to any one of; 5. 1.
  • the top coat layer contains a polycarbonate polyurethane resin. ⁇ 4.
  • the resin beads are urethane beads.
  • the topcoat layer has a dynamic friction coefficient of 0.48 to 0.56.
  • Example 1 First, a surface layer resin solution was prepared. Specifically, 40 parts by mass of dimethylformamide was added to 100 parts by mass of a polycarbonate polyurethane resin (Crisbon S-707 manufactured by DIC Corporation) to adjust the viscosity to about 2000 mPa ⁇ s to obtain a resin solution for the surface layer.
  • a polycarbonate polyurethane resin Carbon S-707 manufactured by DIC Corporation
  • a resin solution for the adhesive layer was prepared. Specifically, for 100 parts by mass of a polycarbonate polyurethane resin (Crisbon TA-205 manufactured by DIC Corporation), 10 parts by mass of a curing agent (NE-crosslinking agent manufactured by Dainichiseika Kogyo Co., Ltd.), a catalyst (manufactured by DIC Corporation) Accelerator F) 1 part by mass and 50 parts by mass of dimethylformamide were added to adjust the viscosity to about 4500 mPa ⁇ s to obtain an adhesive layer resin solution.
  • a polycarbonate polyurethane resin Chemical TA-205 manufactured by DIC Corporation
  • a curing agent NE-crosslinking agent manufactured by Dainichiseika Kogyo Co., Ltd.
  • a catalyst manufactured by DIC Corporation
  • Accelerator F 1 part by mass and 50 parts by mass of dimethylformamide were added to adjust the viscosity to about 4500 mPa ⁇ s to obtain an adhesive layer resin solution.
  • the resin solution for the surface layer prepared above is applied to a release paper having unevennesses formed on the surface with a height of 10 ⁇ m and a width of 300 ⁇ m (the distance between the apexes of adjacent protrusions). After coating with a comma coater, it was dried at 130° C. for 2 minutes to obtain a surface layer with a thickness of 30 ⁇ m.
  • the unevenness height and unevenness width of the release substrate are values obtained according to the same rules as the arithmetic average roughness Ra of the surface of the topcoat layer and the average spacing S of the convex portions, respectively. Yes, measured according to JIS B0601 1994.
  • a topcoat layer resin solution was prepared according to the following recipe: Polycarbonate polyurethane resin (trade name PERMUTEX EX-RU-13-085F, manufactured by Stahl Japan Co., Ltd., solid content 30% by mass): 220 parts by mass Resin beads (urethane beads, average particle size 7 ⁇ m, dynamic beads UCN-5070D, Dainichiseika Kogyo Co., Ltd., solid content 100% by mass): 7.5 parts by mass Crosslinking agent (PERMUTEX XR-5508, Stahl Japan Co., Ltd., solid content 40% by mass): 4 parts by mass Water: Appropriate amount.
  • Polycarbonate polyurethane resin trade name PERMUTEX EX-RU-13-085F, manufactured by Stahl Japan Co., Ltd., solid content 30% by mass
  • Resin beads urethane beads, average particle size 7 ⁇ m, dynamic beads UCN-5070D, Dainichiseika Kogyo Co., Ltd., solid content 100% by mass
  • the release paper is removed, the surface layer is coated with the resin solution for the top coat layer with a reverse roll coater, and then dried at 130 ° C. for 2 minutes to form a top coat layer with a thickness of 8 ⁇ m. Then, the skin material of Example 1 was obtained.
  • Example 2 [Examples 2 to 9, Comparative Examples 1 to 5]
  • the release paper was changed to have the unevenness height and unevenness width shown in Table 1 below, and the average particle diameter and addition amount (content) of the resin beads were changed as shown in Table 1 below.
  • Skin materials of Examples 2 to 9 and Comparative Examples 1 to 5 were produced in the same manner as in Example 1, except that the
  • each panelist rated the roughness and smoothness on a 6-point scale from 0 (rough) to 5 (smooth) in 1-point increments, and the dry and wet feeling on a 1-point scale from 0 (smooth) to 5 (moist).
  • a score was given in 6 stages of increments. The average score was used as the evaluation result.
  • Table 1 below.
  • ⁇ , ⁇ , and ⁇ conform to the following criteria. If it is ⁇ or ⁇ , it can be used without problems.
  • [Appearance evaluation] 10 panelists were shown the skin materials prepared in each example and comparative example, and the appearance of the outermost surface of the skin material was like genuine leather or like resin. Asked. Table 1 shows the evaluation results according to the following criteria. In addition, in the following criteria, if ⁇ or ⁇ , it was considered as a pass: ⁇ : 8 or more people answered that the appearance was like genuine leather, ⁇ : 5 to 7 people answered that the appearance was like genuine leather, x: 4 or less people answered that the appearance was like genuine leather.
  • the dynamic friction coefficient ⁇ d of the surface of the topcoat layer was measured for the skin materials produced in each of the examples and comparative examples.
  • a robot arm type friction characteristic measuring machine manufactured by Sintokagaku Co., Ltd. was used.
  • a spherical indenter (10 mm in diameter) was used as the indenter, with a load of 200 g and a speed of 50 mm/sec. The results are shown in Table 1 below.
  • ⁇ , ⁇ or ⁇ was regarded as a pass: ⁇ : ⁇ d is 0.48 or more, ⁇ : ⁇ d is 0.40 or more and less than 0.48, ⁇ : ⁇ d is 0.35 or more and less than 0.40, x: ⁇ d is less than 0.35.
  • the skin materials of Examples 1 to 9, in which the topcoat layer has a predetermined surface roughness and an average distance between protrusions and contain resin beads having a predetermined average particle diameter are rough and smooth. It was found to have excellent tactile sensation and high dryness and wetness.
  • Comparative Example 1 in which the surface roughness is larger than a predetermined value
  • Comparative Examples 2 and 3 in which the average distance between the convex portions is not predetermined, and the average particle diameter of the resin beads is larger than the predetermined value.
  • Comparative Example 5 which had a large amount, the rough and smooth feeling was low.
  • Comparative Example 4 in which the average particle size of the resin beads was smaller than the predetermined value, the feeling of dryness and humidity was low.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Mechanical Engineering (AREA)
PCT/IB2022/000707 2021-12-08 2022-12-07 表皮材料 Ceased WO2023105285A1 (ja)

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EP22903648.8A EP4446112A4 (en) 2021-12-08 2022-12-07 Skin material
CN202280080418.0A CN118354903A (zh) 2021-12-08 2022-12-07 表皮材料
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003127258A (ja) 2001-10-19 2003-05-08 Dainippon Printing Co Ltd 離型シート及びそれを用いて製造された合成皮革
JP2006305733A (ja) * 2005-03-31 2006-11-09 Nissan Motor Co Ltd 表皮材
JP2009282511A (ja) * 2008-04-22 2009-12-03 Fujifilm Corp 防眩フィルム、反射防止フィルム、偏光板及び画像表示装置
JP2010082960A (ja) * 2008-09-30 2010-04-15 Nissan Motor Co Ltd 自動車内装用表皮
WO2017168980A1 (ja) * 2016-03-29 2017-10-05 シーアイ化成株式会社 化粧シート
CN111051605A (zh) * 2017-09-14 2020-04-21 乐金华奥斯株式会社 人造革及其制造方法
KR20200131774A (ko) * 2019-05-14 2020-11-24 (주)엘지하우시스 인조가죽, 이로부터 제조된 크래쉬 패드 스킨 및 이의 제조방법
JP2021115714A (ja) * 2020-01-22 2021-08-10 三菱ケミカル株式会社 樹脂積層体、仕切り材、及び樹脂積層体の製造方法
WO2021246470A1 (ja) * 2020-06-03 2021-12-09 凸版印刷株式会社 化粧シート

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008302549A (ja) * 2007-06-06 2008-12-18 Nissan Motor Co Ltd 表皮材、その製造方法及び自動車内装用表皮材
CN102691216B (zh) * 2011-03-25 2015-12-02 东洋纺织株式会社 汽车内饰材料用合成皮革
JP2014065983A (ja) * 2012-09-25 2014-04-17 Seiren Co Ltd 合成皮革及びその製造方法
JP6660143B2 (ja) * 2015-10-22 2020-03-04 株式会社クラレ 撥水性皮革様シート

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003127258A (ja) 2001-10-19 2003-05-08 Dainippon Printing Co Ltd 離型シート及びそれを用いて製造された合成皮革
JP2006305733A (ja) * 2005-03-31 2006-11-09 Nissan Motor Co Ltd 表皮材
JP2009282511A (ja) * 2008-04-22 2009-12-03 Fujifilm Corp 防眩フィルム、反射防止フィルム、偏光板及び画像表示装置
JP2010082960A (ja) * 2008-09-30 2010-04-15 Nissan Motor Co Ltd 自動車内装用表皮
WO2017168980A1 (ja) * 2016-03-29 2017-10-05 シーアイ化成株式会社 化粧シート
CN111051605A (zh) * 2017-09-14 2020-04-21 乐金华奥斯株式会社 人造革及其制造方法
KR20200131774A (ko) * 2019-05-14 2020-11-24 (주)엘지하우시스 인조가죽, 이로부터 제조된 크래쉬 패드 스킨 및 이의 제조방법
JP2021115714A (ja) * 2020-01-22 2021-08-10 三菱ケミカル株式会社 樹脂積層体、仕切り材、及び樹脂積層体の製造方法
WO2021246470A1 (ja) * 2020-06-03 2021-12-09 凸版印刷株式会社 化粧シート

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4446112A4

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CN118354903A (zh) 2024-07-16

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