WO2010073949A1 - Leather-like sheet and method for producing same - Google Patents

Leather-like sheet and method for producing same Download PDF

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Publication number
WO2010073949A1
WO2010073949A1 PCT/JP2009/070990 JP2009070990W WO2010073949A1 WO 2010073949 A1 WO2010073949 A1 WO 2010073949A1 JP 2009070990 W JP2009070990 W JP 2009070990W WO 2010073949 A1 WO2010073949 A1 WO 2010073949A1
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WO
WIPO (PCT)
Prior art keywords
hot
polyurethane
melt
type moisture
melt type
Prior art date
Application number
PCT/JP2009/070990
Other languages
French (fr)
Japanese (ja)
Inventor
久夫 米田
善典 金川
実 鷹嘴
淑文 玉木
Original Assignee
株式会社クラレ
Dic株式会社
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Application filed by 株式会社クラレ, Dic株式会社 filed Critical 株式会社クラレ
Priority to JP2010544020A priority Critical patent/JP5635414B2/en
Publication of WO2010073949A1 publication Critical patent/WO2010073949A1/en

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/26—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on a rotating drum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/30—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. moulding around inserts or for coating articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
    • B29C41/32—Making multilayered or multicoloured articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/10—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • 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
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
    • D06N3/0095—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique by inversion technique; by transfer processes
    • D06N3/0097—Release surface, e.g. separation sheets; Silicone papers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/554—Wear resistance
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/748—Releasability
    • 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
    • B32B2375/00—Polyureas; Polyurethanes
    • 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
    • B32B2437/00—Clothing
    • 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
    • B32B2437/00—Clothing
    • B32B2437/02—Gloves, shoes
    • 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
    • B32B2439/00—Containers; Receptacles
    • 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
    • B32B2479/00—Furniture
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/02—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by a sequence of laminating steps, e.g. by adding new layers at consecutive laminating stations
    • B32B37/025—Transfer laminating

Definitions

  • the present invention relates to a leather-like sheet comprising a polyurethane laminate and a method for producing the same.
  • a leather-like sheet made of a polyurethane laminate has been widely used as a surface material for footwear, clothing, bags, furniture, and the like.
  • a composite fiber base material in which a fibrous base material such as a nonwoven fabric, a woven fabric, or a knitted fabric is impregnated with polyurethane is used as a base fabric, and the surface of such a base fabric is used.
  • the intermediate layer is formed by applying a solvent-type polyurethane or water-based polyurethane to the surface of the base fabric and then drying, or by adhering a polyurethane film previously formed on the surface of the release paper to the surface of the base fabric with an adhesive. It is formed using.
  • Patent Document 1 discloses a method of using a hot-melt moisture-curing polyurethane as a method for producing a leather-like sheet that can reduce the amount of organic solvent used.
  • FIG. 3 of Patent Document 1 describes a method of bonding a film layer made of hot-melt type moisture-curing polyurethane on a substrate with an adhesive made of hot-melt type moisture-curing polyurethane. ing.
  • this method will be described in detail.
  • FIG. 1 shows a drawing quoting [FIG. 3] described in Patent Document 1.
  • 30 is a delivery reel of release paper (release paper) 301
  • 36 is a delivery reel of a base material 37
  • 38 is a take-up reel of a leather-like sheet as a product
  • 31, 32, 33a, 33b, 34 , 35 are rollers
  • 303 and 305 are knife coaters for applying hot-melt type moisture-curing polyurethanes 312 and 313
  • 304 is a steam sprayer.
  • the release paper 301 wound around the delivery reel 30 is carried on rollers 31 and 32. Then, a coating layer is formed by applying a hot-melt type moisture-curing polyurethane 312 in a molten state to the surface of the release paper 301 with a knife coater 303. Subsequently, water vapor is sprayed onto the film layer made of the hot-melt type moisture-curing polyurethane 312 with the water vapor sprayer 304.
  • a hot-melt type moisture-curing polyurethane 313 in a molten state is further applied as an adhesive on the coating layer made of the hot-melt type moisture-curing polyurethane 312 with the knife coater 305 To do.
  • the base material 37 is supplied from the delivery reel 36, and the base material 37 is bonded to the adhesive layer of the hot-melt type moisture-cure polyurethane with the roller 35 to manufacture a leather-like sheet.
  • the hot-melt moisture-curing polyurethane is applied to the substrate by heating and melting, and then solidified by being cooled to a predetermined temperature after application. By having such heat melting property, excellent coating workability is exhibited.
  • a film layer made of hot-melt type moisture-cured polyurethane 312 applied in a molten state to the surface of the release paper 301 is sprayed with water vapor by a water vapor sprayer 304, and then a roller 33a. , 33b and sent to the roller 34.
  • the curing reaction is accelerated by spraying water vapor.
  • the curing reaction does not proceed sufficiently, so that adhesiveness (tack) remains on the surface. And tackiness is suppressed because hardening reaction advances with high molecular weight with the injected water vapor
  • the coating layer formed from the hot melt moisture-curing polyurethane 312 is sufficiently crosslinked and cured by reducing the line feed rate, the tack is reduced to some extent and the transportability is improved to some extent. Is done.
  • the adhesion with the layer made of the hot-melt type moisture-curing polyurethane 313 to be laminated was not sufficiently high. This is because when an intermediate layer made of hot-melt type moisture-cured polyurethane is further laminated on the skin layer made of hot-melt type moisture-cured polyurethane that has undergone a curing reaction to some extent, This is probably because the formation of a clear interface between them decreases the peel strength at the interface.
  • the present invention provides a polyurethane having a good process passability and a high peel strength at the laminated portion in the production of a leather-like sheet having a skin layer and an intermediate layer made of hot-melt type moisture-curing polyurethane on a base fabric. It aims at providing the method of manufacturing the leather-like sheet
  • One aspect of the present invention is that a first application step of applying heat-melted first hot-melt type moisture-cure polyurethane to the surface of the first sheet, and the applied first hot-melt type moisture-cure polyurethane are melted Or the 2nd application process of apply
  • Another aspect of the present invention is a leather-like sheet obtained by the above production method.
  • FIG. 1 is a drawing in which [FIG. 3] described in Patent Document 1 is cited.
  • FIG. 2 is a schematic process diagram illustrating a method for manufacturing a leather-like sheet according to the first embodiment.
  • FIG. 3 is a schematic process diagram illustrating a manufacturing method according to a modification of the first embodiment.
  • FIG. 4 is a schematic cross-sectional view of the leather-like sheet obtained by the process of the first embodiment.
  • the method for producing a leather-like sheet of the present invention includes a first application step of applying a first hot-melt type moisture-cured polyurethane, which is heated and melted, to the surface of the first sheet, and the applied first hot-melt type moisture.
  • a second application step of applying a second hot-melt type moisture-cure polyurethane heated and melted on the surface of the cured polyurethane in a melted or softened state; and the applied second hot-melt type moisture-cure polyurethane The manufacturing method of a polyurethane laminated body provided with the bonding process which bonds a 2nd sheet
  • seat, or the base fabric (base material) already formed with the polyurethane layer etc. Is used.
  • a release paper, a polyurethane film with a release paper, or the like can be used for the other sheet.
  • FIG. 2 is a schematic process diagram illustrating a method for producing a polyurethane laminate according to this embodiment.
  • 1 is a release paper
  • 2 is a first hot melt type moisture curing polyurethane
  • 3 is a second hot melt type moisture curing polyurethane
  • 4 is a base fabric.
  • Reference numeral 11 denotes a delivery reel of the release paper 1
  • 12 denotes a delivery reel of the base cloth 4
  • 13 denotes a take-up reel of the leather-like sheet 10.
  • 2a is a knife coater
  • 3a is a roll coater
  • 2b and 3b are resin feeders each having a heater (not shown).
  • the knife coater 2a and the roll coater 3a are sequentially arranged around the main roll R rotating in the direction of the arrow in FIG. Further, a calendar roll CR is provided for bonding the base fabric 4 delivered from the delivery reel 12 to the surface of the molten second hot-melt moisture-curing polyurethane 2.
  • the release paper 1 is continuously fed from the feed reel 11, conveyed by the main roll R rotating in the direction of the arrow, and then wound by the take-up reel 13 to form a line.
  • the first hot-melt moisture-curing polyurethane 2 accommodated in the resin feeder 2b and heated and melted flows down toward the release paper 1 on the line while maintaining the molten state, and the release paper is supplied by the knife coater 2a. It is applied to one surface with a uniform thickness (first application step).
  • a release paper having an embossed pattern may be used in addition to a smooth release paper for the purpose of imparting surface design.
  • the hot-melt type moisture-cure polyurethane is a polyurethane-forming component having a heat melting property and a moisture-curing property containing a urethane prepolymer obtained by reacting a polyol and a polyisocyanate as a main component.
  • Hot melt moisture-curing polyurethane has a heat-melting property that is solid at room temperature or has a viscosity that is difficult to apply. It solidifies and develops adhesiveness. As described above, the hot-melt moisture-curing polyurethane is applied to a base fabric or a release paper by being melted by heating, and after being applied, it is solidified by being cooled.
  • the moisture (humidity) curability of the hot melt moisture-curing polyurethane is based on a curing reaction in which the isocyanate group terminal in the urethane prepolymer and moisture (water) react to form a urethane bond or a urea bond.
  • the curability of the hot-melt type moisture-curing polyurethane depends on a crosslinking reaction caused by the reaction of the formed urethane bond or urea bond with an isocyanate group present in the system. Then, through such a curing reaction and a crosslinking reaction, the urethane prepolymer has a high molecular weight, whereby a polyurethane cured product having excellent mechanical properties and water resistance is formed.
  • the moisture curing reaction of the hot melt moisture-curing polyurethane is completely cured over a relatively long period of time, specifically, for example, about 20 to 50 hours. Therefore, immediately after being heated and melted and applied, and immediately after cooling and solidifying, adhesiveness (tackiness) remains on the surface. Then, by aging for about 20 to 50 hours under predetermined temperature and humidity conditions, the crosslinking reaction proceeds to increase the molecular weight. And tackiness disappears.
  • urethane prepolymer contained in the hot-melt type moisture-curing polyurethane as described above those obtained by reacting polyol and polyisocyanate can be used.
  • polyester polyol for example, polyester polyol, polyether polyol, polycarbonate polyol and the like can be used.
  • polyether polyol especially polytetramethylene glycol.
  • polycarbonate polyol when the leather-like sheet is used for a car seat or a furniture member, it is preferable to use polycarbonate polyol because high durability (heat resistance, hydrolysis resistance, etc.) is required.
  • the polyether polyol and polycarbonate polyol such as polytetramethylene glycol are preferably used in an amount of 40% by mass or more based on the total amount of polyol used.
  • polyisocyanate that reacts with the polyol examples include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexa Polymers such as dimers and trimers of aliphatic diisocyanates such as methylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and the like, and alicyclic diisocyanates, 4,4′-diphenylmethane diisocyanate Use diphenylmethane diisocyanate, etc.
  • aromatic diisocyanates such as
  • naphthalene diisocyanate and xylylene diisocyanate which are non-yellowing polyisocyanates with excellent light resistance, from the viewpoint of preventing yellowing due to light
  • aromatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.
  • the production of the urethane prepolymer can usually be carried out in the absence of a solvent, but it may be carried out in an organic solvent.
  • an organic solvent such as ethyl acetate, n-butyl acetate, methyl ethyl ketone, and toluene that does not inhibit the reaction between the polyol and the polyisocyanate can be used. It is necessary to remove the organic solvent later by a method such as heating under reduced pressure.
  • the number average molecular weight of the urethane prepolymer in the hot melt moisture-curing polyurethane is preferably in the range of 500 to 30,000, more preferably 1000 to 10,000.
  • the urethane prepolymer contained in the first hot-melt type moisture-curing polyurethane has a number average molecular weight in the range of 500 to 5,000 and is contained in the second hot-melt type moisture-curing polyurethane.
  • the urethane prepolymer having a number average molecular weight in the range of 600 to 30,000 is preferable from the viewpoint that the melt viscosity resulting from workability can be easily adjusted.
  • the melt viscosity of the hot-melt type moisture-curing polyurethane is 100 to 100 for both the first hot-melt type moisture-curing polyurethane and the second hot-melt type moisture-curing polyurethane.
  • the range of 15000 mPa ⁇ s, more preferably in the range of 1000 to 10000 mPa ⁇ s is preferable because it can be applied as a thin film.
  • the hot-melt type moisture-curing polyurethane in the present embodiment is usually a resin component mainly composed of a urethane prepolymer, a urethanization catalyst, a colorant such as a pigment, a thickener, a crosslinking agent, a crosslinking accelerator, an oxidation agent. Used as a resin composition containing additives such as an inhibitor. Moreover, when it is desired to form a polyurethane layer formed from hot-melt moisture-curing polyurethane as a foamed polyurethane layer, a foaming agent is blended. Such a resin composition can be obtained by uniformly mixing a resin component mainly composed of a urethane prepolymer and other components in a heated and melted state.
  • the coating mechanism for applying hot melt type moisture-curing polyurethane to the surface of the release paper 1 by heating and melting in addition to the knife coater and roll coater as shown in FIG. 2, for example, reverse roll coater and reverse coater A kiss roll coater, a spray coater, a T-die coater, a comma coater or the like can be used.
  • the application mechanism provided with the heating means is preferable from the point that the melt viscosity of the hot-melt type moisture-curing polyurethane can be controlled.
  • the melt viscosity of the first hot-melt moisture-curing polyurethane at the time of application is preferably in the range of 1000 to 15000 mPa ⁇ s, more preferably 2000 to 10000 mPa ⁇ s, from the viewpoint of excellent coating workability.
  • the thickness of the polyurethane layer formed from the first hot-melt type moisture-cured polyurethane is excellent in flexibility and mechanical strength when it is in the range of 5 to 800 ⁇ m, more preferably 10 to 500 ⁇ m after curing. This is preferable from the viewpoint of obtaining a leather-like sheet.
  • the second hot-melt type moisture-cure polyurethane that is heated and melted is applied to the surface (first). 2 application process).
  • the release paper 1 coated with the first hot melt type moisture curing polyurethane 2 is conveyed in the direction of the roll coater 3a for applying the second hot melt type moisture curing polyurethane 3 by the main roll R rotating in the direction of the arrow. Is done. And the 2nd hot-melt type moisture hardening polyurethane 3 accommodated in the resin feeder 3b is apply
  • the state in which the hot-melt type moisture-curing polyurethane is melted or softened means a state in which the hot-melt type moisture-curing polyurethane that has been melted by heating is not solidified.
  • the moisture-curing polyurethane itself retains fluidity, or the hot-melt moisture-curing polyurethane retains fluidity due to external force, or at least partially retains fluidity.
  • the melt viscosity of the first hot-melt type moisture-cure polyurethane is higher than the melt viscosity of the second hot-melt type moisture-cure polyurethane.
  • the melt viscosity of the first hot-melt type moisture-curing polyurethane is adjusted to be in the range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-curing polyurethane.
  • the second hot-melt type moisture-cure polyurethane is applied to a coating layer made of the first hot-melt type moisture-cure polyurethane in a molten or softened state.
  • the melt viscosity of the first hot melt moisture-curing polyurethane when applying the second hot melt moisture-curing polyurethane is too low, the first hot melt moisture-curing polyurethane and the second hot melt polyurethane There is a tendency that the two-layer structure cannot be sufficiently maintained due to mixing with the melt-type moisture-curing polyurethane. From this point, in the second coating step, the melt viscosity of the first hot-melt type moisture-curing polyurethane is in the range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-curing polyurethane. Is more preferable.
  • melt viscosity can be performed, for example, as follows.
  • the first hot melt type moisture curing polyurethane 2 is applied by a knife coater 2a
  • the second hot melt type moisture curing polyurethane 3 is applied by a roll coater 3a.
  • the temperature of the knife coater 2a and the roll coater 3a is controlled by a heater (not shown), respectively, so that the first hot-melt type moisture-curing polyurethane 2 and the second hot-melt type moisture-curing polyurethane in the second coating step. 3 melt viscosity can be controlled.
  • the main roll R is used using the integrated application
  • the first moisture-curing polyurethane 2 is accommodated in the upstream resin supply part 22b with respect to the rotation direction of the main roll R, and the second moisture-curing polyurethane 3 is accommodated in the resin supply part 23b downstream with respect to the rotation direction of the main roll R.
  • the melt viscosity when applying the second hot-melt type moisture-curing polyurethane is preferably in the range of 1000 to 10000 mPa ⁇ s, more preferably 2000 to 7000 mPa ⁇ s, from the viewpoint of excellent coating workability.
  • the melt viscosity of the first hot-melt type moisture-curing polyurethane is preferably 1500 to 15000 mPa ⁇ s, more preferably 3500 to 14000 mPa ⁇ s.
  • the thickness of the polyurethane layer formed from the second hot-melt type moisture-cured polyurethane should be in the range of 5 to 800 ⁇ m, more preferably 10 to 500 ⁇ m as the thickness after curing, in terms of flexibility and mechanical strength. This is preferable because an excellent leather-like sheet can be obtained.
  • the base fabric 4 is sent out from the delivery reel 12 and bonded by the calender roll CR in a state where the applied second hot-melt type moisture-curing polyurethane 3 is melted or softened.
  • the base fabric 4 used in the present embodiment include, for example, fiber base materials generally used for leather-like sheets such as non-woven fabrics, woven fabrics, and knitted fabrics; Examples thereof include composite fiber base materials impregnated with water-based, emulsion-based or solvent-free polyurethane resins, acrylic resins, butadiene-based resins (SBR, NBR, MBR) and the like.
  • the composite fiber base material which impregnated the polyurethane resin to the nonwoven fabric formed from the ultrafine fiber is used especially preferable from the point from which the leather-like sheet
  • nonwoven fabric a conventionally known short fiber web, a web obtained by a known method such as a spunbond method or a melt blow method can be used without any particular limitation. Moreover, after forming a web as needed, you may obtain by laminating
  • the fibers forming the nonwoven fabric include, for example, polyurethane fibers, polyethylene terephthalate (PET) fibers, various polyamide fibers, polyacrylic fibers, various polyolefin fibers, and polyvinyl alcohol fibers.
  • the fibers forming the nonwoven fabric are preferably ultrafine fibers having a fiber diameter of 0.1 to 50 ⁇ m, more preferably 1 to 15 ⁇ m. Such ultrafine fibers are preferred because they have a low rigidity and are soft, so that a leather-like sheet having a soft texture can be obtained.
  • the basis weight of the nonwoven fabric is preferably in the range of 50 to 2000 g / m 2 , more preferably in the range of 100 to 1000 g / m 2 , from the viewpoint of obtaining a leather-like sheet having a soft texture and excellent process passability.
  • seat 10 is formed by sticking the base fabric 4 on the surface of the 2nd hot-melt type moisture hardening polyurethane 3 of a molten or softened state with the calendar roll CR. Then, the obtained leather-like sheet 10 is taken up by the take-up reel 13 while being covered with the release paper 1.
  • the moisture hardening reaction of the 1st hot melt type moisture hardening polyurethane 2 and the 2nd hot melt type moisture hardening polyurethane 3 advances by curing the wound leather-like sheet 10 for a predetermined time, and hot
  • the melt-type moisture-cured polyurethane has a high molecular weight.
  • the aging conditions of the obtained leather-like sheet 10 are preferably aging for about 20 to 50 hours at a temperature of 20 to 40 ° C. and a relative humidity of 50 to 80%.
  • the hot-melt type moisture-curing polyurethane is moisture-cured and moisture-crosslinked.
  • seat excellent in mechanical strength and water resistance is obtained.
  • the first hot-melt type moisture-curing polyurethane is not particularly limited as long as the second hot-melt type moisture-curing polyurethane heated and melted can be applied to the surface in a melted or softened state. It is preferably within 1 m, and more preferably within 50 cm, in that the first hot-melt type moisture-cured polyurethane can stably maintain the melted or softened state.
  • the second moisture-curing polyurethane 3 is applied in a heated and melted state before re-solidifying.
  • the polyurethane layer formed from the first hot-melt type moisture-curing polyurethane 2 and the polyurethane layer formed from the second hot-melt type moisture-curing polyurethane 3 are cross-linked with each other, and the peel strength at the interface is high.
  • the curing reaction of the first hot-melt type moisture-cured polyurethane 2 in a molten or softened state does not proceed sufficiently. Therefore, the first hot-melt type moisture-cure polyurethane 2 and the second hot-melt type moisture-cure polyurethane 3 form a sufficient cross-linked structure at their interface, and the interface of these layers is obscured. Can do.
  • the leather-like sheet 10 is completed by peeling the release paper 1 coated on the surface.
  • the release paper 1 is sent out as the first sheet from the delivery reel 11 and the base cloth 4 is sent out as the second sheet from the delivery reel 12.
  • the supply of the release paper 1 and the supply of the base cloth 4 are performed.
  • the base cloth 4 may be sent out as a first sheet from the delivery reel 11 and the release paper 1 may be sent out as a second sheet from the delivery reel 12 by changing the order.
  • a hot melt type moisture hardening polyurethane is used as a base fabric or a release paper. After the coating, the first hot-melt type moisture-curing polyurethane is melted or softened, and the second hot-melt type moisture-curing polyurethane in a heat-melted state is applied without particular limitation. sell.
  • the leather-like sheet thus obtained has a first polyurethane layer formed from the first hot-melt type moisture-cure polyurethane 2 and a second polyurethane layer formed from the second hot-melt type moisture-cure polyurethane 3. Can maintain high adhesion. For this reason, in the obtained leather-like sheet, the appearance and texture with fine creases and uniform uniformity are improved.
  • the surface layer portion is made of a solvent-based, water-based, emulsion-based or solvent-free polyurethane resin or acrylic resin. Coating or post-processing such as buffing or embossing may be appropriately performed.
  • the leather-like sheet thus obtained can be preferably used as a leather-like sheet that becomes a surface material for footwear, clothing, bags, furniture, and the like.
  • the melt viscosity (mPa ⁇ s) of each hot-melt moisture-curing polyurethane was measured using a cone plate viscometer (manufactured by ICI) with the cone plate temperature set to a predetermined temperature.
  • the melt viscosity of the second hot melt moisture-curing polyurethane in the second coating step was defined as the melt viscosity of the second hot melt moisture-curing polyurethane at the coating temperature (knife coater temperature) in the second coating step. .
  • melt viscosity of the first hot-melt type moisture-curing polyurethane in the second coating step is the surface of the applied first hot-melt type moisture-curing polyurethane immediately before the second hot-melt type moisture-curing polyurethane is applied. The temperature was measured and taken as the melt viscosity at that temperature.
  • ⁇ Base fabric> A water-soluble polyurethane (Hydran WLS612 manufactured by DIC Corporation) was impregnated into an entangled nonwoven fabric made of ultrafine fibers having an average fineness of 0.07 dtex.
  • Tyforth EXP-BH50 hot melt type moisture-cured polyurethane manufactured by DIC Corporation
  • POLYTON PU-9382 BLACK manufactured by DIC Corporation, the same applies hereinafter
  • Example 1 A leather-like sheet was manufactured using a manufacturing process as shown in FIG.
  • the release paper 1 is continuously fed out from the feed reel 11 as a first sheet at a speed of 1 m / min, conveyed by the main roll R rotating in the direction of the arrow, and taken up by the take-up reel 13 to form a line. Formed.
  • the surface temperature of the main roll R was controlled to be 50 ° C.
  • the hot melt type moisture curing polyurethane A accommodated in the resin feeder 2b as the first hot melt type moisture curing polyurethane 2 flows down in a state melted at 110 ° C.
  • the coater 2a was applied to the surface of the release paper 1 with a uniform thickness (first application step).
  • the surface temperature of the knife coater 2a was controlled at 110 ° C. with a heater (not shown). At this time, the gap between the knife coater 2a and the release paper was adjusted to 50 ⁇ m.
  • the hot melt type moisture cured polyurethane A applied to the surface of the release paper 1 is melted at 135 ° C. as the second hot melt type moisture cured polyurethane 3 on the surface thereof.
  • Moisture-cure polyurethane C was applied (second application step).
  • the surface temperature of the roll coater 3a was controlled to 135 ° C. by a heater (not shown).
  • the gap between the roll coater 3a and the release paper was adjusted to 250 ⁇ m.
  • the surface temperature of the applied hot melt moisture-curing polyurethane A was about 120 ° C., and the melt viscosity at that time was about 5000 mPa ⁇ s.
  • melt viscosity at 135 ° C. of the hot-melt type moisture-cure polyurethane C was about 2500 mPa ⁇ s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about twice the melt viscosity of the hot melt moisture-curing polyurethane C.
  • the base fabric 4 as the second sheet was bonded to the surface of the applied hot-melt type moisture-cure polyurethane C in a molten state (bonding step).
  • the base fabric 4 was sent out from the delivery reel 12 and bonded with a calendar roll CR in a state where the hot-melt moisture-cure polyurethane C was melted.
  • the surface temperature of the calendar roll CR was controlled at 50 ° C. by a heater (not shown). In this way, a leather-like sheet 10 having a layer structure as shown in FIG. 4 was formed. Then, the obtained leather-like sheet was wound up by the take-up reel 13 while being covered with a release paper.
  • the leather-like sheet 10 was aged for 35 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 60%. After aging, the obtained leather-like sheet 10 was cut by a predetermined area, the release paper was peeled off, and interlayer adhesion was evaluated by the following method.
  • the peel strength of the obtained leather-like sheet was 11.0 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric.
  • Example 2 The manufacturing process as shown in FIG. 3 with different application mechanisms was used, and the hot-melt moisture-cure polyurethane B was used as the first hot-melt moisture-cure polyurethane 2. A leather-like sheet was manufactured.
  • an integrated coating mechanism 25 including two knife coaters 22a and 23a and two resin supply portions 22b and 23b for storing hot-melt type moisture-cure polyurethane is used.
  • the resin supply unit 22b stores hot melt type moisture curing polyurethane B as the first hot melt type moisture curing polyurethane 2
  • the resin supply unit 23b stores the second hot melt type moisture curing polyurethane 3 as the hot melt type moisture curing polyurethane 3. Mold moisture cured polyurethane C was housed.
  • the release paper 1 was continuously sent out from the delivery reel 11 as a first sheet at a speed of 1 m / min, conveyed by the main roll R rotating in the direction of the arrow, and taken up by the take-up reel 13 to form a line.
  • the surface temperature of the main roll R was controlled to be 50 ° C.
  • the hot melt moisture-curing polyurethane B accommodated in the resin supply unit 22b flows down toward the release paper 1 on the line in a melted state, and the knife coater 22a has a uniform thickness on the surface of the release paper 1 It applied (first application process).
  • the hot-melt type moisture-cure polyurethane C accommodated in the resin supply unit 23b was flowed down in a molten state and applied with a uniform thickness by the knife coater 23a (second application step).
  • the gap between the knife coater 22a and the release paper surface was adjusted to 50 ⁇ m, and the gap between the knife coater 23a and the release paper surface was adjusted to 250 ⁇ m.
  • the knife coater 22a and the resin supply unit 22b were controlled at 110 ° C., and the knife coater 23a and the resin supply unit 23b were controlled at 120 ° C.
  • the surface temperature of the hot-melt type moisture-cured polyurethane B applied in the first application step was about 110 ° C., and the melt viscosity at that time was about 5000 mPa ⁇ s. Further, the melt viscosity at 120 ° C. of the hot-melt type moisture-cure polyurethane C was about 3200 mPa ⁇ s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane B in the second coating step was about 1.6 times the melt viscosity of the hot melt moisture-curing polyurethane C.
  • Example 2 The subsequent steps were performed in the same manner as in Example 1 to produce a leather-like sheet.
  • the peel strength of the obtained leather-like sheet was 10.2 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric.
  • Example 3 In the first coating step, the hot-melt type moisture-curing polyurethane A is flowed down in a melted state at 100 ° C., and in the second coating step, the hot-melt type moisture-curing polyurethane C is flowed down in a melted state at 140 ° C. Produced a leather-like sheet in the same manner as in Example 1. At this time, the surface temperature of the roll coater 3a was controlled to 140 ° C. by a heater (not shown).
  • the melt viscosity of the hot-melt type moisture-cured polyurethane A applied in the first coating step is about 6500 mPa ⁇ s
  • the melt viscosity of the hot-melt type moisture-cured polyurethane C is about 6500 mPa ⁇ s.
  • the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about 3.6 times the melt viscosity of the hot melt moisture-curing polyurethane C.
  • Example 4 In the first coating step, the hot-melt type moisture-curing polyurethane A flows down in a state melted at 120 ° C., and in the second coating step, the hot-melt type moisture-curing polyurethane C flows down in a state melted at 115 ° C. Produced a leather-like sheet in the same manner as in Example 1. At this time, the surface temperature of the roll coater 3a was controlled to 115 ° C. by a heater (not shown).
  • the melt viscosity of the hot-melt type moisture-cured polyurethane A applied in the first coating step is about 2700 mPa ⁇ s
  • the melt viscosity of the hot-melt type moisture-cured polyurethane C is about 2700 mPa ⁇ s.
  • the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about 0.7 times the melt viscosity of the hot melt moisture-curing polyurethane C.
  • the peel strength of the obtained leather-like sheet was 10.6 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric.
  • the polyurethane layer formed from the hot-melt type moisture-curing polyurethane A and the polyurethane layer formed from the hot-melt type moisture-curing polyurethane C were partially mixed.
  • the release paper 1 was fed from the feed reel 30 toward the take-up reel 38 at a speed of 1 m / min to form a line. Then, the release paper 1 wound around the delivery reel 30 was carried on rollers 31 and 32. And the coating layer was formed by apply
  • the first hot-melt type moisture-curing polyurethane 2 was partially left on the surface. Therefore, the laminated intermediate body is wound around the rollers 33a and 33b shown in FIG.
  • the obtained leather-like sheet was aged for 35 hours under conditions of a temperature of 40 ° C. and a relative humidity of 60%. Then, after aging, the obtained leather-like sheet was cut by a predetermined area, the release paper was peeled off, and the interlayer adhesion was evaluated by the same method as in Example 1. As a result, the peel strength of the leather-like sheet was 6.5 kg / 25 mm, and interface peeling occurred at the interface between the layer made of hot-melt type moisture-curing polyurethane A and the layer made of hot-melt type moisture-curing polyurethane B. It was.
  • the leather-like sheets obtained in Examples 1 to 4 according to the present invention all had high peel strength.
  • Examples 1 to 2, and 4 no peeling was observed at the interface between the polyurethane layers. This is probably because the two types of hot-melt type moisture-cured polyurethane are laminated in a molten state, so that the interface becomes unclear and a sufficient crosslinked structure is formed at the interface.
  • Example 3 some peeling was partially also at the interface between the polyurethane layer formed from the hot-melt type moisture-curing polyurethane A and the polyurethane layer formed from the hot-melt type moisture-curing polyurethane C. Although seen, the peel strength was sufficiently high.
  • Comparative Example 1 when the hot-melt type moisture-curing polyurethane A was applied and re-solidified, the tackiness remained and the continuous production was difficult. Further, as in Comparative Example 2, when the hot melt moisture-curing polyurethane A was applied and produced on a low-speed line that solidified to such an extent that tack was eliminated, the peel strength was remarkably low. This is presumably because the interface between the two polyurethane layers became clear and a sufficient crosslinked structure was not formed between the two layers.
  • the first hot-melt type moisture-cured polyurethane heated and melted is applied to the surface of the first sheet, and the first hot-melt applied
  • a second application step of applying a second hot-melt type moisture-curing polyurethane heated and melted on the surface of the mold-moisture-curing polyurethane in a melted or softened state, and the applied second hot-melt type moisture It is a manufacturing method of a leather-like sheet provided with the pasting process of pasting the 2nd sheet on the surface in the state where hardened polyurethane has melted or softened.
  • the peel strength at the interface is increased by forming an interface in which the first hot-melt type moisture-cured polyurethane and the second hot-melt type moisture-cured polyurethane are cross-linked with each other. . Further, by making it difficult to form a clear interface formed by the above-described conventional manufacturing method, the interface becomes unclear and the peel strength at the interface becomes higher.
  • the first hot-melt type moisture-cured polyurethane in the melted or softened state is coated with the second hot-melt type moisture-cured polyurethane before the curing reaction sufficiently proceeds. A sufficient cross-linked structure can be formed between the layer formed by the moisture-cured polyurethane and the layer formed by the second hot-melt type moisture-cured polyurethane.
  • the surface of the layer made of the first hot-melt type moisture-curing polyurethane and the layer made of the second hot-melt type moisture-curing polyurethane are coated with the first sheet and the second sheet, respectively. Therefore, tack derived from uncured hot melt moisture-cured polyurethane does not appear. Therefore, the process passability is also excellent.
  • the melt viscosity of the first hot melt moisture-curing polyurethane is higher than the melt viscosity of the second hot melt moisture-curing polyurethane, and further, the first hot melt
  • the melt viscosity of the moisture-curing polyurethane is preferably 1.5 to 2 times the melt viscosity of the second hot-melt moisture-curing polyurethane.
  • first hot-melt type moisture-curing polyurethane and / or the second hot-melt type moisture-curing polyurethane contains a foaming agent
  • an elastic polyurethane layer used as an intermediate layer can be easily formed. Can be formed.
  • the leather-like sheet obtained by any one of the above production methods is a second polyurethane layer formed from the first polyurethane layer formed from the first hot melt type moisture cured polyurethane and the second hot melt type moisture cured polyurethane.
  • the polyurethane layer can maintain high adhesion and unity. For this reason, the obtained leather-like sheet has fine creases and is excellent in uniform appearance and texture.
  • a method for producing a leather-like sheet that can sufficiently enhance the peel strength at the interface between two polyurethane laminates formed from hot-melt moisture-cured polyurethane.

Abstract

Disclosed is a method for producing a leather-like sheet that is characterized by comprising a first application step, in which a heated and melted first hot-melt, moisture-curing polyurethane is applied to the surface of a first sheet, a second application step, in which a heated and melted second hot-melt, moisture-curing polyurethane is applied to that surface in a state in which the aforementioned first hot-melt, moisture-curing polyurethane that had been applied has been melted or softened, and a gluing step, in which a second sheet is glued to that surface in a state in which the aforementioned second hot-melt, moisture-curing polyurethane that had been applied has been melted or softened.

Description

皮革様シート及びその製造方法Leather-like sheet and manufacturing method thereof
　本発明は、ポリウレタン積層体からなる皮革様シート及びその製造方法に関する。 The present invention relates to a leather-like sheet comprising a polyurethane laminate and a method for producing the same.
　従来から、履物、衣類、鞄、家具等の表面素材としてポリウレタン積層体からなる皮革様シートが広く用いられている。 Conventionally, a leather-like sheet made of a polyurethane laminate has been widely used as a surface material for footwear, clothing, bags, furniture, and the like.
　このような皮革様シートの代表的な構成としては、不織布，織布，編布等の繊維質基材にポリウレタン等を含浸させた複合繊維基材を基布とし、このような基布表面に、ポリウレタンからなる中間層を積層した後、形成された中間層表面にさらにポリウレタンやアクリル樹脂等から形成される銀面層を形成したような構成が挙げられる。該中間層は、基布表面に、溶剤型ポリウレタンや水系ポリウレタンを塗布した後、乾燥する方法や、基布表面に、予め離型紙表面に成膜されたポリウレタン膜を接着剤により接着する方法を用いて形成されている。 As a typical configuration of such a leather-like sheet, a composite fiber base material in which a fibrous base material such as a nonwoven fabric, a woven fabric, or a knitted fabric is impregnated with polyurethane is used as a base fabric, and the surface of such a base fabric is used. An example is a structure in which after an intermediate layer made of polyurethane is laminated, a silver surface layer formed of polyurethane, acrylic resin or the like is further formed on the surface of the formed intermediate layer. The intermediate layer is formed by applying a solvent-type polyurethane or water-based polyurethane to the surface of the base fabric and then drying, or by adhering a polyurethane film previously formed on the surface of the release paper to the surface of the base fabric with an adhesive. It is formed using.
　ところで、近年、環境負荷を低減させるために、ポリウレタン製品の生産分野において、有機溶剤を大量に使用しない水性ポリウレタンや無溶剤型ポリウレタンを用いたプロセスが求められている。皮革様シートの製造においても水系ポリウレタンを用いたプロセスが、一部、実用化されている。しかしながら、水系ポリウレタンは、耐水性や耐久性等が劣る点、あるいは、乾燥効率が低い点等から、溶剤型ポリウレタンを充分に置き換えるには至っていない。 By the way, in recent years, in order to reduce the environmental burden, in the polyurethane product production field, a process using an aqueous polyurethane or a solventless polyurethane which does not use a large amount of an organic solvent is required. In the production of leather-like sheets, some processes using water-based polyurethane have been put into practical use. However, water-based polyurethanes have not yet sufficiently replaced solvent-based polyurethanes due to poor water resistance, durability, etc., or low drying efficiency.
　例えば、下記特許文献１には、有機溶剤の使用量を低減しうる皮革様シートの製造方法としてホットメルト型湿分硬化ポリウレタンを用いる方法が開示されている。具体的には、特許文献１の［図３］には、基材上にホットメルト型湿分硬化ポリウレタンからなる皮膜層をホットメルト型湿分硬化ポリウレタンからなる接着剤で接着する方法が記載されている。以下、この方法を詳しく説明する。 For example, Patent Document 1 below discloses a method of using a hot-melt moisture-curing polyurethane as a method for producing a leather-like sheet that can reduce the amount of organic solvent used. Specifically, [FIG. 3] of Patent Document 1 describes a method of bonding a film layer made of hot-melt type moisture-curing polyurethane on a substrate with an adhesive made of hot-melt type moisture-curing polyurethane. ing. Hereinafter, this method will be described in detail.
　図１に、特許文献１に記載された［図３］を引用した図面を示す。図１中、３０は剥離紙（離型紙）３０１の送り出しリール、３６は基材３７の送り出しリール、３８は製品である皮革様シートの巻き取りリールであり、３１，３２，３３ａ，３３ｂ，３４，３５はローラー、３０３及び３０５はホットメルト型湿分硬化ポリウレタン３１２，３１３をそれぞれ塗布するためのナイフコーター、３０４は水蒸気噴霧器である。 FIG. 1 shows a drawing quoting [FIG. 3] described in Patent Document 1. In FIG. 1, 30 is a delivery reel of release paper (release paper) 301, 36 is a delivery reel of a base material 37, 38 is a take-up reel of a leather-like sheet as a product, 31, 32, 33a, 33b, 34 , 35 are rollers, 303 and 305 are knife coaters for applying hot-melt type moisture- curing polyurethanes 312 and 313, and 304 is a steam sprayer.
　図１においては、送り出しリール３０に巻かれた剥離紙３０１を、ローラー３１、３２に乗せて搬送する。そして、ナイフコーター３０３で剥離紙３０１表面に溶融状態のホットメルト型湿分硬化ポリウレタン３１２を塗布することにより皮膜層を形成する。続いて、ホットメルト型湿分硬化ポリウレタン３１２からなる皮膜層に、水蒸気噴霧器３０４で水蒸気を吹きつける。そして、ローラー３３ａ，３３ｂに乗せてローラー３４に送りこみ、ナイフコーター３０５でホットメルト型湿分硬化ポリウレタン３１２からなる皮膜層上にさらに接着剤として溶融状態のホットメルト型湿分硬化ポリウレタン３１３を塗布する。そして、送り出しリール３６から基材３７を供給し、ローラー３５でホットメルト型湿分硬化ポリウレタンの接着層に基材３７を貼り合わせて皮革様シートを製造している。 In FIG. 1, the release paper 301 wound around the delivery reel 30 is carried on rollers 31 and 32. Then, a coating layer is formed by applying a hot-melt type moisture-curing polyurethane 312 in a molten state to the surface of the release paper 301 with a knife coater 303. Subsequently, water vapor is sprayed onto the film layer made of the hot-melt type moisture-curing polyurethane 312 with the water vapor sprayer 304. Then, it is placed on the rollers 33a and 33b and sent to the roller 34, and a hot-melt type moisture-curing polyurethane 313 in a molten state is further applied as an adhesive on the coating layer made of the hot-melt type moisture-curing polyurethane 312 with the knife coater 305 To do. Then, the base material 37 is supplied from the delivery reel 36, and the base material 37 is bonded to the adhesive layer of the hot-melt type moisture-cure polyurethane with the roller 35 to manufacture a leather-like sheet.
特開２０００－５４２７２号公報JP 2000-54272 A
　特許文献１に記載されたような無溶剤型のホットメルト型湿分硬化ポリウレタンを用いて皮膜層や接着剤層を形成した場合には、確かに、無溶剤化を実現しうる。しかしながら、上記のような方法を用いて、工業的に皮革様シートを連続生産する場合、次のような問題があった。 In the case where a film layer or an adhesive layer is formed using a solvent-free hot-melt type moisture-cure polyurethane as described in Patent Document 1, it is possible to realize solvent-free. However, when a leather-like sheet is industrially continuously produced using the method as described above, there are the following problems.
　ホットメルト型湿分硬化ポリウレタンは、加熱溶融することにより基材に塗布され、塗布後に所定の温度にまで冷却されることにより再固化する。このような熱溶融性を有することにより、優れた塗布作業性を発揮する。 The hot-melt moisture-curing polyurethane is applied to the substrate by heating and melting, and then solidified by being cooled to a predetermined temperature after application. By having such heat melting property, excellent coating workability is exhibited.
　図１に示したようなプロセスにおいては、剥離紙３０１表面に溶融状態で塗布されたホットメルト型湿分硬化ポリウレタン３１２からなる皮膜層は、水蒸気噴霧器３０４で水蒸気を吹きつけられた後、ローラー３３ａ，３３ｂに乗せられてローラー３４に送りこまれる。このような工程においては、水蒸気を吹きつけることにより硬化反応が促進される。なお、水蒸気を吹きつけられた直後においては、硬化反応は充分に進行していないために、その表面には粘着性（タック）が残っている。そして、噴射された水蒸気等により硬化反応が進んで高分子量化されることにより、タック性が抑制される。そして、硬化反応を促進させてタック性を抑制することによりスムーズな搬送性を確保しようとしていると思われる。しかしながら、短時間では硬化反応が完全には進行しないために、ある程度のタック性が残る。そのために、ホットメルト型湿分硬化ポリウレタン３１２から形成された皮膜層が、ローラー３３ａ，３３ｂの表面と接触した場合、ホットメルト型湿分硬化ポリウレタン３１２に残るタックにより、ホットメルト型湿分硬化ポリウレタン３１２の皮膜層がローラー３３ａ，３３ｂの表面に付着してローラー３３ａ，３３ｂに巻き付いて、スムーズな搬送を阻害するという問題が生じる。また、ラインの送り速度を低速にすることにより、ホットメルト型湿分硬化ポリウレタン３１２から形成された皮膜層をより充分に架橋硬化させた場合には、タックがある程度少なくなって搬送性はある程度改善される。しかしながらこの場合には、積層されるホットメルト型湿分硬化ポリウレタン３１３からなる層との接着性が充分に高いものにならなかった。これは、ある程度硬化反応が進行したホットメルト型湿分硬化ポリウレタンからなる表皮層に、さらにホットメルト型湿分硬化ポリウレタンからなる中間層を積層しようとした場合には、表皮層と中間層との間に明確な界面が形成されることにより、界面における剥離強度が低くなるためであると思われる。 In the process as shown in FIG. 1, a film layer made of hot-melt type moisture-cured polyurethane 312 applied in a molten state to the surface of the release paper 301 is sprayed with water vapor by a water vapor sprayer 304, and then a roller 33a. , 33b and sent to the roller 34. In such a process, the curing reaction is accelerated by spraying water vapor. Immediately after the water vapor is blown, the curing reaction does not proceed sufficiently, so that adhesiveness (tack) remains on the surface. And tackiness is suppressed because hardening reaction advances with high molecular weight with the injected water vapor | steam etc., and tackiness is suppressed. And it seems that smooth conveyance property is going to be ensured by accelerating hardening reaction and suppressing tackiness. However, since the curing reaction does not proceed completely in a short time, some tackiness remains. Therefore, when the film layer formed from the hot-melt type moisture-curing polyurethane 312 comes into contact with the surfaces of the rollers 33a and 33b, the hot-melt type moisture-curing polyurethane 312 has a tack that remains on the hot-melt-type moisture-curing polyurethane 312. The film layer 312 adheres to the surfaces of the rollers 33a and 33b and wraps around the rollers 33a and 33b, thereby causing a problem of hindering smooth conveyance. In addition, when the coating layer formed from the hot melt moisture-curing polyurethane 312 is sufficiently crosslinked and cured by reducing the line feed rate, the tack is reduced to some extent and the transportability is improved to some extent. Is done. However, in this case, the adhesion with the layer made of the hot-melt type moisture-curing polyurethane 313 to be laminated was not sufficiently high. This is because when an intermediate layer made of hot-melt type moisture-cured polyurethane is further laminated on the skin layer made of hot-melt type moisture-cured polyurethane that has undergone a curing reaction to some extent, This is probably because the formation of a clear interface between them decreases the peel strength at the interface.
　このように、ホットメルト型湿分硬化ポリウレタンを用いて工業的なプロセスにおいて皮革様シートを連続生産する場合、ローラー等によるスムーズな搬送が阻害され、また積層体の接着性が充分に高いものにならないという問題があった。 As described above, when leather-like sheets are continuously produced in an industrial process using hot-melt type moisture-cured polyurethane, smooth conveyance by rollers or the like is hindered, and the laminate has sufficiently high adhesion. There was a problem of not becoming.
　本発明は、基布上にホットメルト型湿分硬化ポリウレタンからなる表皮層と中間層とを有する皮革様シートを製造する場合において、工程通過性が良好で、かつ積層部分の剥離強度が高いポリウレタン積層体からなる皮革様シートを製造する方法を提供することを目的とする。 The present invention provides a polyurethane having a good process passability and a high peel strength at the laminated portion in the production of a leather-like sheet having a skin layer and an intermediate layer made of hot-melt type moisture-curing polyurethane on a base fabric. It aims at providing the method of manufacturing the leather-like sheet | seat which consists of a laminated body.
　本発明の一局面は、加熱溶融させた第１ホットメルト型湿分硬化ポリウレタンを第１シートの表面に塗布する第１塗布工程と、塗布された前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布する第２塗布工程と、塗布された前記第２ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に第２シートを貼り合せる貼合工程とを備えることを特徴とする皮革様シートの製造方法である。 One aspect of the present invention is that a first application step of applying heat-melted first hot-melt type moisture-cure polyurethane to the surface of the first sheet, and the applied first hot-melt type moisture-cure polyurethane are melted Or the 2nd application process of apply | coating the 2nd hot-melt type moisture hardening polyurethane heat-melted on the surface in the softened state, and the applied said 2nd hot-melt type moisture hardening polyurethane melt | dissolve or soften It is a manufacturing method of the leather-like sheet | seat characterized by including the bonding process of bonding a 2nd sheet | seat on the surface in the state which is carrying out.
　また、本発明の他の一局面は、上記の製造方法により得られた皮革様シートである。 Further, another aspect of the present invention is a leather-like sheet obtained by the above production method.
　本発明の目的、特徴、局面、及び利点は、以下の詳細な説明と添付図面とによって、より明白となる。 The objects, features, aspects, and advantages of the present invention will become more apparent from the following detailed description and the accompanying drawings.
図１は、特許文献１に記載された［図３］を引用した図面である。FIG. 1 is a drawing in which [FIG. 3] described in Patent Document 1 is cited. 図２は、第１実施形態の皮革様シートの製造方法を説明する模式工程図である。FIG. 2 is a schematic process diagram illustrating a method for manufacturing a leather-like sheet according to the first embodiment. 図３は、第１実施形態の変形例の製造方法を説明する模式工程図である。FIG. 3 is a schematic process diagram illustrating a manufacturing method according to a modification of the first embodiment. 図４は、第１実施形態の工程により得られた皮革様シートの断面模式図である。FIG. 4 is a schematic cross-sectional view of the leather-like sheet obtained by the process of the first embodiment.
　本発明の皮革様シートの製造方法は、加熱溶融させた第１ホットメルト型湿分硬化ポリウレタンを第１シートの表面に塗布する第１塗布工程と、塗布された前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布する第２塗布工程と、塗布された前記第２ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に第２シートを貼り合せる貼合工程とを備えるポリウレタン積層体の製造方法を含むものである。なお、前記第１シート及び第２シートとしては、何れか一方のシートに、皮革様シートの製造において用いられる基布（基材）または既にポリウレタン層が形成されている基布（基材）等が用いられる。また、他の一方のシートに、離型紙や離型紙付ポリウレタン膜等が用いられうる。 The method for producing a leather-like sheet of the present invention includes a first application step of applying a first hot-melt type moisture-cured polyurethane, which is heated and melted, to the surface of the first sheet, and the applied first hot-melt type moisture. A second application step of applying a second hot-melt type moisture-cure polyurethane heated and melted on the surface of the cured polyurethane in a melted or softened state; and the applied second hot-melt type moisture-cure polyurethane The manufacturing method of a polyurethane laminated body provided with the bonding process which bonds a 2nd sheet | seat on the surface in the state melt | dissolved or softened. In addition, as said 1st sheet | seat and 2nd sheet | seat, the base fabric (base material) used in manufacture of a leather-like sheet | seat in any one sheet | seat, or the base fabric (base material) already formed with the polyurethane layer etc. Is used. Moreover, a release paper, a polyurethane film with a release paper, or the like can be used for the other sheet.
　以下、本発明の一実施形態を、図２を参照しながら説明する。 Hereinafter, an embodiment of the present invention will be described with reference to FIG.
　図２は、本実施形態のポリウレタン積層体の製造方法を説明する模式工程図である。図２中、１は離型紙、２は第１ホットメルト型湿分硬化ポリウレタン、３は第２ホットメルト型湿分硬化ポリウレタン、４は基布である。また、１１は離型紙１の送り出しリール、１２は基布４の送り出しリール、１３は皮革様シート１０の巻き取りリールである。また、２ａはナイフコーター、３ａはロールコーターであり、２ｂ，３ｂは図略のヒーターを備えた樹脂フィーダーである。ナイフコーター２ａ及びロールコーター３ａは、図２中矢印方向に回転する主ロールＲの周囲に回転方向に順に配設されている。また、送り出しリール１２から送り出された基布４を溶融状態の第２のホットメルト型湿分硬化ポリウレタン２の表面に貼り合せるためのカレンダーロールＣＲが配設されている。 FIG. 2 is a schematic process diagram illustrating a method for producing a polyurethane laminate according to this embodiment. In FIG. 2, 1 is a release paper, 2 is a first hot melt type moisture curing polyurethane, 3 is a second hot melt type moisture curing polyurethane, and 4 is a base fabric. Reference numeral 11 denotes a delivery reel of the release paper 1, 12 denotes a delivery reel of the base cloth 4, and 13 denotes a take-up reel of the leather-like sheet 10. Further, 2a is a knife coater, 3a is a roll coater, and 2b and 3b are resin feeders each having a heater (not shown). The knife coater 2a and the roll coater 3a are sequentially arranged around the main roll R rotating in the direction of the arrow in FIG. Further, a calendar roll CR is provided for bonding the base fabric 4 delivered from the delivery reel 12 to the surface of the molten second hot-melt moisture-curing polyurethane 2.
　図２の工程においては、はじめに送り出しリール１１から離型紙１が連続的に送り出され、矢印方向に回転する主ロールＲにより搬送された後、巻き取りリール１３により巻き取られて、ラインが形成される。 In the process of FIG. 2, first, the release paper 1 is continuously fed from the feed reel 11, conveyed by the main roll R rotating in the direction of the arrow, and then wound by the take-up reel 13 to form a line. The
　そして、ライン上の離型紙１に向けて、樹脂フィーダー２ｂ中に収容されて加熱溶融された第１ホットメルト型湿分硬化ポリウレタン２が溶融状態を維持しながら流下され、ナイフコーター２ａにより離型紙１表面に均一な厚みで塗布される（第１塗布工程）。 Then, the first hot-melt moisture-curing polyurethane 2 accommodated in the resin feeder 2b and heated and melted flows down toward the release paper 1 on the line while maintaining the molten state, and the release paper is supplied by the knife coater 2a. It is applied to one surface with a uniform thickness (first application step).
　本実施形態で使用される離型紙１としては、表面平滑な離型紙の他、表面意匠性を付与する目的で、エンボス模様を有するような離型紙を用いてもよい。 As the release paper 1 used in the present embodiment, a release paper having an embossed pattern may be used in addition to a smooth release paper for the purpose of imparting surface design.
　ここで、本実施形態で使用されるホットメルト型湿分硬化ポリウレタンについて説明する。 Here, the hot melt type moisture curing polyurethane used in the present embodiment will be described.
　ホットメルト型湿分硬化ポリウレタンは、ポリオールとポリイソシアネートとを反応させて得られるウレタンプレポリマーを主成分として含有する、熱溶融性と湿分硬化性とを備えたポリウレタン形成成分である。 The hot-melt type moisture-cure polyurethane is a polyurethane-forming component having a heat melting property and a moisture-curing property containing a urethane prepolymer obtained by reacting a polyol and a polyisocyanate as a main component.
　ホットメルト型湿分硬化ポリウレタンが有する熱溶融性は、常温では固体ないしは塗布が困難な程度の粘稠性を有する性質であるが、加熱溶融することにより塗布が可能な粘度になり、冷却により再固化して接着性を発現するものである。このように、ホットメルト型湿分硬化ポリウレタンは、加熱溶融することにより基布や離型紙等に塗布され、塗布された後、冷却されることにより再固化する。 Hot melt moisture-curing polyurethane has a heat-melting property that is solid at room temperature or has a viscosity that is difficult to apply. It solidifies and develops adhesiveness. As described above, the hot-melt moisture-curing polyurethane is applied to a base fabric or a release paper by being melted by heating, and after being applied, it is solidified by being cooled.
　一方、ホットメルト型湿分硬化ポリウレタンが有する湿分（湿気）硬化性は、ウレタンプレポリマー中のイソシアネート基末端と湿気（水）が反応してウレタン結合や尿素結合を形成する硬化反応による。また、ホットメルト型湿分硬化ポリウレタンが有する硬化性は、形成されたウレタン結合や尿素結合が、さらに系内に存在するイソシアネート基と反応することによる架橋反応にもよる。そして、このような硬化反応及び架橋反応を経て、ウレタンプレポリマーが高分子量化することにより機械的特性及び耐水性等に優れたポリウレタン硬化物が形成される。 On the other hand, the moisture (humidity) curability of the hot melt moisture-curing polyurethane is based on a curing reaction in which the isocyanate group terminal in the urethane prepolymer and moisture (water) react to form a urethane bond or a urea bond. Further, the curability of the hot-melt type moisture-curing polyurethane depends on a crosslinking reaction caused by the reaction of the formed urethane bond or urea bond with an isocyanate group present in the system. Then, through such a curing reaction and a crosslinking reaction, the urethane prepolymer has a high molecular weight, whereby a polyurethane cured product having excellent mechanical properties and water resistance is formed.
　ホットメルト型湿分硬化ポリウレタンが有する湿分硬化反応は、短時間で生じる冷却固化とは対照的に、比較的長い時間、具体的には例えば、２０～５０時間程度掛けて完全硬化する。従って、加熱溶融して塗布した後、冷却固化した直後においては、表面に、粘着性（タック性）が残っている。そして、所定の温度及び湿度条件下で２０～５０時間程度熟成させることにより、架橋反応が進行して高分子量化する。そして、タック性が消失する。 In contrast to the cooling and solidification that occurs in a short time, the moisture curing reaction of the hot melt moisture-curing polyurethane is completely cured over a relatively long period of time, specifically, for example, about 20 to 50 hours. Therefore, immediately after being heated and melted and applied, and immediately after cooling and solidifying, adhesiveness (tackiness) remains on the surface. Then, by aging for about 20 to 50 hours under predetermined temperature and humidity conditions, the crosslinking reaction proceeds to increase the molecular weight. And tackiness disappears.
　前記したようなホットメルト型湿分硬化ポリウレタン中に含まれるウレタンプレポリマーとしては、ポリオールとポリイソシアネートとを反応させて得られるものを使用することができる。 As the urethane prepolymer contained in the hot-melt type moisture-curing polyurethane as described above, those obtained by reacting polyol and polyisocyanate can be used.
　前記ポリオールとしては、例えばポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール等を使用することができる。なかでも、本発明で得られた皮革様シートを靴用途に使用する場合には、ポリエーテルポリオール、特にポリテトラメチレングリコールを使用することが好ましい。また、前記皮革様シートをカーシートや家具の部材等に使用する場合には、高耐久性（耐熱性や耐加水分解性等）が求められるため、ポリカーボネートポリオールを使用することが好ましい。前記ポリテトラメチレングリコール等のポリエーテルポリオールやポリカーボネートポリオールは、使用するポリオールの全量に対して４０質量％以上使用することが好ましい。 As the polyol, for example, polyester polyol, polyether polyol, polycarbonate polyol and the like can be used. Especially, when using the leather-like sheet | seat obtained by this invention for shoes uses, it is preferable to use polyether polyol, especially polytetramethylene glycol. Further, when the leather-like sheet is used for a car seat or a furniture member, it is preferable to use polycarbonate polyol because high durability (heat resistance, hydrolysis resistance, etc.) is required. The polyether polyol and polycarbonate polyol such as polytetramethylene glycol are preferably used in an amount of 40% by mass or more based on the total amount of polyol used.
　また、前記ポリオールと反応するポリイソシアネートとしては、例えば、フェニレンジイソシアネート、トリレンジイソシアネート、４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、キシリレンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族ジイソシアネートまたは脂環族ジイソシアネート、４，４’－ジフェニルメタンジイソシアネートの２量体および３量体等のポリメリックジフェニルメタンジイソシアネート等を使用することができる。なかでも、皮革様シートの表皮を形成するためのホットメルト型湿分硬化ポリウレタンとしては、光による黄変色を防止する観点から、耐光性に優れる無黄変ポリイソシアネートであるナフタレンジイソシアネート、キシリレンジイソシアネート等の芳香族ジイソシアネート、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、テトラメチルキシリレンジイソシアネートを使用することが好ましい。 Examples of the polyisocyanate that reacts with the polyol include aromatic diisocyanates such as phenylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, naphthalene diisocyanate, xylylene diisocyanate, hexa Polymers such as dimers and trimers of aliphatic diisocyanates such as methylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate and the like, and alicyclic diisocyanates, 4,4′-diphenylmethane diisocyanate Use diphenylmethane diisocyanate, etc. Can. Among these, as hot-melt type moisture-cured polyurethane for forming the skin of leather-like sheets, naphthalene diisocyanate and xylylene diisocyanate, which are non-yellowing polyisocyanates with excellent light resistance, from the viewpoint of preventing yellowing due to light It is preferable to use aromatic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate.
　前記ウレタンプレポリマーの製造は、通常、無溶剤下で行うことができるが、有機溶剤中で製造してもよい。有機溶剤中で製造する場合には、前記ポリオールとポリイソシアネートとの反応を阻害しない酢酸エチル、酢酸ｎ－ブチル、メチルエチルケトン、トルエン等の有機溶剤を使用することができるが、反応の途中又は反応終了後に減圧加熱等の方法により有機溶剤を除去することが必要である。 The production of the urethane prepolymer can usually be carried out in the absence of a solvent, but it may be carried out in an organic solvent. In the case of producing in an organic solvent, an organic solvent such as ethyl acetate, n-butyl acetate, methyl ethyl ketone, and toluene that does not inhibit the reaction between the polyol and the polyisocyanate can be used. It is necessary to remove the organic solvent later by a method such as heating under reduced pressure.
　前記ポリオールと前記ポリイソシアネートとの反応割合は、前記ポリイソシアネート中のイソシアネート基と、前記ポリオール中の水酸基との当量比［ＮＣＯ／ＯＨ］が、１．１～５．０の範囲内であることが好ましく、１．２～３．０の範囲内であることがより好ましい。前記当量比が１．１以上である場合には、ホットメルト型湿分硬化ポリウレタンの湿気硬化性が良好となる。 The reaction ratio between the polyol and the polyisocyanate is such that the equivalent ratio [NCO / OH] of the isocyanate group in the polyisocyanate to the hydroxyl group in the polyol is in the range of 1.1 to 5.0. Is more preferable, and is more preferably within a range of 1.2 to 3.0. When the equivalent ratio is 1.1 or more, the moisture-curing property of the hot-melt type moisture-curing polyurethane is good.
　ホットメルト型湿分硬化ポリウレタン中のウレタンプレポリマーの数平均分子量としては、５００～３００００、さらには１０００～１００００の範囲であることが好ましい。特に、第１ホットメルト型湿分硬化ポリウレタン中に含まれるウレタンプレポリマーとしては、５００～５０００の範囲の数平均分子量を有するものであることが、第２ホットメルト型湿分硬化ポリウレタン中に含まれるウレタンプレポリマーとしては、６００～３００００の範囲の数平均分子量を有するものであることが、作業性に起因する溶融粘度を容易に調整しうる点から好ましい。ウレタンプレポリマーの数平均分子量がこのような範囲であれば、優れた柔軟性、機械的強度、耐摩耗性、耐加水分解性を有するポリウレタン層を形成することができる。 The number average molecular weight of the urethane prepolymer in the hot melt moisture-curing polyurethane is preferably in the range of 500 to 30,000, more preferably 1000 to 10,000. In particular, the urethane prepolymer contained in the first hot-melt type moisture-curing polyurethane has a number average molecular weight in the range of 500 to 5,000 and is contained in the second hot-melt type moisture-curing polyurethane. The urethane prepolymer having a number average molecular weight in the range of 600 to 30,000 is preferable from the viewpoint that the melt viscosity resulting from workability can be easily adjusted. When the number average molecular weight of the urethane prepolymer is in such a range, a polyurethane layer having excellent flexibility, mechanical strength, abrasion resistance, and hydrolysis resistance can be formed.
　ホットメルト型湿分硬化ポリウレタンの溶融粘度としては、コーンプレート粘度計で測定した１２５℃における溶融粘度が、第１ホットメルト型湿分硬化ポリウレタン及び第２ホットメルト型湿分硬化ポリウレタンともに、１００～１５０００ｍＰａ・ｓ、さらには１０００～１００００ｍＰａ・ｓの範囲であることが薄膜で塗布することが可能であるために好ましい。 As the melt viscosity of the hot-melt type moisture-curing polyurethane, the melt viscosity at 125 ° C. measured with a cone plate viscometer is 100 to 100 for both the first hot-melt type moisture-curing polyurethane and the second hot-melt type moisture-curing polyurethane. The range of 15000 mPa · s, more preferably in the range of 1000 to 10000 mPa · s is preferable because it can be applied as a thin film.
　本実施形態におけるホットメルト型湿分硬化ポリウレタンは、通常、ウレタンプレポリマーを主成分とする樹脂成分の他、ウレタン化触媒、顔料等の着色剤、増粘剤、架橋剤、架橋促進剤、酸化防止剤等の添加剤を配合した樹脂組成物として用いられる。また、ホットメルト型湿分硬化ポリウレタンから形成されるポリウレタン層を発泡ポリウレタン層として形成したい場合には発泡剤が配合される。このような樹脂組成物は、ウレタンプレポリマーを主成分とする樹脂成分とその他の成分を加熱溶融状態で均一に混合させることにより得ることができる。 The hot-melt type moisture-curing polyurethane in the present embodiment is usually a resin component mainly composed of a urethane prepolymer, a urethanization catalyst, a colorant such as a pigment, a thickener, a crosslinking agent, a crosslinking accelerator, an oxidation agent. Used as a resin composition containing additives such as an inhibitor. Moreover, when it is desired to form a polyurethane layer formed from hot-melt moisture-curing polyurethane as a foamed polyurethane layer, a foaming agent is blended. Such a resin composition can be obtained by uniformly mixing a resin component mainly composed of a urethane prepolymer and other components in a heated and melted state.
　ホットメルト型湿分硬化ポリウレタンを加熱溶融させて離型紙１表面に塗布する塗布機構の具体例としては、図２に示したようなナイフコーターやロールコーターの他、例えば、リバースロールコーター、リバースコーター、キスロールコーター、スプレーコーター、Ｔ－ダイコーター、又はコンマコーター等が用いられうる。なお、これらの塗布機構においては、ホットメルト型湿分硬化ポリウレタンの溶融粘度を制御しうる点から、加熱手段を備えた塗布機構が好ましい。 As a specific example of the coating mechanism for applying hot melt type moisture-curing polyurethane to the surface of the release paper 1 by heating and melting, in addition to the knife coater and roll coater as shown in FIG. 2, for example, reverse roll coater and reverse coater A kiss roll coater, a spray coater, a T-die coater, a comma coater or the like can be used. In addition, in these application mechanisms, the application mechanism provided with the heating means is preferable from the point that the melt viscosity of the hot-melt type moisture-curing polyurethane can be controlled.
　塗布時の第１ホットメルト型湿分硬化ポリウレタンの溶融粘度としては、１０００～１５０００ｍＰａ・ｓ、さらには２０００～１００００ｍＰａ・ｓの範囲であることが塗装作業性に優れている点から好ましい。 The melt viscosity of the first hot-melt moisture-curing polyurethane at the time of application is preferably in the range of 1000 to 15000 mPa · s, more preferably 2000 to 10000 mPa · s, from the viewpoint of excellent coating workability.
　第１ホットメルト型湿分硬化ポリウレタンから形成されるポリウレタン層の厚みとしては、硬化後の厚みとして、５～８００μｍ、さらには１０～５００μｍの範囲であることが柔軟性と機械的強度に優れた皮革様シートが得られる点から好ましい。 The thickness of the polyurethane layer formed from the first hot-melt type moisture-cured polyurethane is excellent in flexibility and mechanical strength when it is in the range of 5 to 800 μm, more preferably 10 to 500 μm after curing. This is preferable from the viewpoint of obtaining a leather-like sheet.
　次に、離型紙１表面に塗布された第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布する（第２塗布工程）。 Next, in a state where the first hot-melt type moisture-cure polyurethane applied to the surface of the release paper 1 is melted or softened, the second hot-melt type moisture-cure polyurethane that is heated and melted is applied to the surface (first). 2 application process).
　第１ホットメルト型湿分硬化ポリウレタン２が塗布された離型紙１は、矢印方向に回転する主ロールＲにより、第２ホットメルト型湿分硬化ポリウレタン３を塗布するためのロールコーター３ａ方向に搬送される。そして、樹脂フィーダー３ｂに収容された第２ホットメルト型湿分硬化ポリウレタン３は、ロールコーター３ａにより溶融状態で均一な厚みに塗布される。このとき、離型紙１表面に塗布された第１ホットメルト型湿分硬化ポリウレタン２は溶融又は軟化状態に維持されている。なお、第２ホットメルト型湿分硬化ポリウレタン３としては、上述した第１ホットメルト型湿分硬化ポリウレタン２で用いたものと同様のものが用いられうる。 The release paper 1 coated with the first hot melt type moisture curing polyurethane 2 is conveyed in the direction of the roll coater 3a for applying the second hot melt type moisture curing polyurethane 3 by the main roll R rotating in the direction of the arrow. Is done. And the 2nd hot-melt type moisture hardening polyurethane 3 accommodated in the resin feeder 3b is apply | coated to the uniform thickness by a roll coater 3a in a molten state. At this time, the first hot-melt moisture-curing polyurethane 2 applied to the surface of the release paper 1 is maintained in a molten or softened state. In addition, as the 2nd hot-melt type moisture hardening polyurethane 3, the thing similar to what was used by the 1st hot-melt type moisture hardening polyurethane 2 mentioned above can be used.
　ここで、ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態とは、加熱溶融されたホットメルト型湿分硬化ポリウレタンが固化していない状態を意味し、具体的には、上記ホットメルト型湿分硬化ポリウレタン自体が流動性を保持している状態若しくは上記ホットメルト型湿分硬化ポリウレタンが外力により流動性を保持している状態、または、それらが少なくとも部分的に流動性を保持している状態を意味する。更に具体的には、流動性を維持している状態としては、溶融粘度として１５０００ｍＰａ・ｓ以下、さらには１００００ｍＰａ・ｓ以下のような状態を維持していることが好ましい。 Here, the state in which the hot-melt type moisture-curing polyurethane is melted or softened means a state in which the hot-melt type moisture-curing polyurethane that has been melted by heating is not solidified. The moisture-curing polyurethane itself retains fluidity, or the hot-melt moisture-curing polyurethane retains fluidity due to external force, or at least partially retains fluidity. Means the state. More specifically, as a state of maintaining fluidity, it is preferable to maintain a melt viscosity of 15000 mPa · s or less, more preferably 10000 mPa · s or less.
　なお、第２塗布工程においては、第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が前記第２ホットメルト型湿分硬化ポリウレタンの溶融粘度よりも高いことが好ましい。また、とくには、第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が、第２ホットメルト型湿分硬化ポリウレタンの溶融粘度の１．５～２倍の範囲になるように調整されていることが好ましい。第２ホットメルト型湿分硬化ポリウレタンは、溶融又は軟化状態にある第１ホットメルト型湿分硬化ポリウレタンからなる塗布層に塗布される。この場合において、第２ホットメルト型湿分硬化ポリウレタンを塗布する際の第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が低すぎる場合には、第１ホットメルト型湿分硬化ポリウレタンと第２ホットメルト型湿分硬化ポリウレタンとが混ざってしまい、２層構造を充分に維持できなくなる傾向がある。このような点から、第２塗布工程において、第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が、第２ホットメルト型湿分硬化ポリウレタンの溶融粘度の１．５～２倍の範囲であることがより好ましい。 In the second coating step, it is preferable that the melt viscosity of the first hot-melt type moisture-cure polyurethane is higher than the melt viscosity of the second hot-melt type moisture-cure polyurethane. In particular, the melt viscosity of the first hot-melt type moisture-curing polyurethane is adjusted to be in the range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-curing polyurethane. preferable. The second hot-melt type moisture-cure polyurethane is applied to a coating layer made of the first hot-melt type moisture-cure polyurethane in a molten or softened state. In this case, if the melt viscosity of the first hot melt moisture-curing polyurethane when applying the second hot melt moisture-curing polyurethane is too low, the first hot melt moisture-curing polyurethane and the second hot melt polyurethane There is a tendency that the two-layer structure cannot be sufficiently maintained due to mixing with the melt-type moisture-curing polyurethane. From this point, in the second coating step, the melt viscosity of the first hot-melt type moisture-curing polyurethane is in the range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-curing polyurethane. Is more preferable.
　このような溶融粘度の調整は、例えば、以下のようにして行うことができる。 Such adjustment of melt viscosity can be performed, for example, as follows.
　図２においては、第１ホットメルト型湿分硬化ポリウレタン２はナイフコーター２ａにより塗布されており、第２ホットメルト型湿分硬化ポリウレタン３はロールコーター３ａにより塗布されている。この場合において、ナイフコーター２ａやロールコーター３ａの温度を図略のヒーターによりそれぞれ制御することにより、第２塗布工程における第１ホットメルト型湿分硬化ポリウレタン２や第２ホットメルト型湿分硬化ポリウレタン３の溶融粘度を制御することができる。 In FIG. 2, the first hot melt type moisture curing polyurethane 2 is applied by a knife coater 2a, and the second hot melt type moisture curing polyurethane 3 is applied by a roll coater 3a. In this case, the temperature of the knife coater 2a and the roll coater 3a is controlled by a heater (not shown), respectively, so that the first hot-melt type moisture-curing polyurethane 2 and the second hot-melt type moisture-curing polyurethane in the second coating step. 3 melt viscosity can be controlled.
　また、別の形態としては、図３に示すように、樹脂供給部２２ｂ及びナイフコーター２２ａと、樹脂供給部２３ｂとナイフコーター２３ａと、を備える一体化された塗布機構２５を用い、主ロールＲの回転方向に対して上流側の樹脂供給部２２ｂに第１湿分硬化ポリウレタン２を収納し、主ロールＲの回転方向に対して下流側の樹脂供給部２３ｂに第２湿分硬化ポリウレタン３を収納する。このとき、第１湿分硬化ポリウレタン２として溶融粘度が相対的に高い湿分硬化ポリウレタンを用い、第２湿分硬化ポリウレタン３として溶融粘度が相対的に低いホットメルト型湿分硬化ポリウレタンを用いる。このように、予め、溶融粘度特性が異なるホットメルト型湿分硬化ポリウレタンを組み合わせて用いることにより、第２塗布工程における第１ホットメルト型湿分硬化ポリウレタン２や第２ホットメルト型湿分硬化ポリウレタン３の溶融粘度を調整してもよい。 Moreover, as another form, as shown in FIG. 3, the main roll R is used using the integrated application | coating mechanism 25 provided with the resin supply part 22b and the knife coater 22a, the resin supply part 23b, and the knife coater 23a. The first moisture-curing polyurethane 2 is accommodated in the upstream resin supply part 22b with respect to the rotation direction of the main roll R, and the second moisture-curing polyurethane 3 is accommodated in the resin supply part 23b downstream with respect to the rotation direction of the main roll R. Store. At this time, a moisture-cured polyurethane having a relatively high melt viscosity is used as the first moisture-cured polyurethane 2, and a hot-melt type moisture-cured polyurethane having a relatively low melt viscosity is used as the second moisture-cured polyurethane 3. In this way, the first hot melt type moisture curing polyurethane 2 and the second hot melt type moisture curing polyurethane in the second application step are used in advance by combining hot melt type moisture curing polyurethanes having different melt viscosity characteristics. The melt viscosity of 3 may be adjusted.
　第２ホットメルト型湿分硬化ポリウレタンを塗布する際の溶融粘度としては、１０００～１００００ｍＰａ・ｓ、さらには２０００～７０００ｍＰａ・ｓの範囲であることが塗装作業性に優れている点から好ましい。 The melt viscosity when applying the second hot-melt type moisture-curing polyurethane is preferably in the range of 1000 to 10000 mPa · s, more preferably 2000 to 7000 mPa · s, from the viewpoint of excellent coating workability.
　また、第２塗布工程において、第１ホットメルト型湿分硬化ポリウレタンの溶融粘度は、１５００～１５０００ｍＰａ・ｓ、さらには、３５００～１４０００ｍＰａ・ｓであることが好ましい。 In the second application step, the melt viscosity of the first hot-melt type moisture-curing polyurethane is preferably 1500 to 15000 mPa · s, more preferably 3500 to 14000 mPa · s.
　また、第２ホットメルト型湿分硬化ポリウレタンから形成されるポリウレタン層の厚みとしては、硬化後の厚みとして、５～８００μｍ、さらには１０～５００μｍの範囲であることが柔軟性と機械的強度に優れた皮革様シートが得られる点から好ましい。 In addition, the thickness of the polyurethane layer formed from the second hot-melt type moisture-cured polyurethane should be in the range of 5 to 800 μm, more preferably 10 to 500 μm as the thickness after curing, in terms of flexibility and mechanical strength. This is preferable because an excellent leather-like sheet can be obtained.
　次に、塗布された第２ホットメルト型湿分硬化ポリウレタン３が溶融又は軟化している状態でその表面に第２シートである基布４を貼り合せる貼合工程について説明する。 Next, a bonding process for bonding the base fabric 4 as the second sheet to the surface of the applied second hot-melt type moisture-curing polyurethane 3 in a melted or softened state will be described.
　具体的には、送り出しリール１２から基布４が送り出され、塗布された第２ホットメルト型湿分硬化ポリウレタン３が溶融又は軟化している状態でカレンダーロールＣＲにより貼り合わされる。 Specifically, the base fabric 4 is sent out from the delivery reel 12 and bonded by the calender roll CR in a state where the applied second hot-melt type moisture-curing polyurethane 3 is melted or softened.
　本実施形態で使用される基布４の具体例としては、例えば、不織布や織布、編布等の一般的に皮革様シートに用いられている繊維基材；上記繊維基材に溶剤系、水系、エマルジョン系又は無溶剤系のポリウレタン樹脂、アクリル樹脂、及びブタジエン系樹脂（ＳＢＲ、ＮＢＲ、ＭＢＲ）等を含浸させた複合繊維基材等が挙げられる。これらの中では、柔軟な風合いとより優れた機械的強度を有する皮革様シートが得られる点から、極細繊維から形成された不織布にポリウレタン樹脂を含浸させた複合繊維基材が特に好ましく用いられる。不織布としては、従来から知られた短繊維ウェブ、スパンボンド法やメルトブロー法等の公知の方法により得られたウェブが特に限定なく用いられうる。また、必要に応じて、ウェブを形成した後、複数枚のウェブを重ねてニードルパンチ処理等により絡合させて得られるものであってもよい。不織布を形成する繊維の具体例としては、例えば、ポリウレタン繊維、ポリエチレンテレフタレート（ＰＥＴ）繊維、各種ポリアミド系繊維、ポリアクリル系繊維、各種ポリオレフィン系繊維、ポリビニルアルコール系繊維等が挙げられる。不織布を形成する繊維は、繊維径が０．１～５０μｍ、さらには１～１５μｍであるような極細繊維であることが好ましい。このような極細繊維は剛性が低く、柔らかいために、柔軟な風合いを有する皮革様シートが得られる点から好ましい。不織布の目付けとしては５０～２０００ｇ／ｍ２の範囲、さらには１００～１０００ｇ／ｍ２の範囲であることが、柔軟な風合いの皮革様シートが得られる点及び工程通過性に優れる点から好ましい。 Specific examples of the base fabric 4 used in the present embodiment include, for example, fiber base materials generally used for leather-like sheets such as non-woven fabrics, woven fabrics, and knitted fabrics; Examples thereof include composite fiber base materials impregnated with water-based, emulsion-based or solvent-free polyurethane resins, acrylic resins, butadiene-based resins (SBR, NBR, MBR) and the like. In these, the composite fiber base material which impregnated the polyurethane resin to the nonwoven fabric formed from the ultrafine fiber is used especially preferable from the point from which the leather-like sheet | seat which has a soft texture and more excellent mechanical strength is obtained. As the nonwoven fabric, a conventionally known short fiber web, a web obtained by a known method such as a spunbond method or a melt blow method can be used without any particular limitation. Moreover, after forming a web as needed, you may obtain by laminating | stacking several webs and making it intertwined by a needle punch process etc. Specific examples of the fibers forming the nonwoven fabric include, for example, polyurethane fibers, polyethylene terephthalate (PET) fibers, various polyamide fibers, polyacrylic fibers, various polyolefin fibers, and polyvinyl alcohol fibers. The fibers forming the nonwoven fabric are preferably ultrafine fibers having a fiber diameter of 0.1 to 50 μm, more preferably 1 to 15 μm. Such ultrafine fibers are preferred because they have a low rigidity and are soft, so that a leather-like sheet having a soft texture can be obtained. The basis weight of the nonwoven fabric is preferably in the range of 50 to 2000 g / m 2 , more preferably in the range of 100 to 1000 g / m 2 , from the viewpoint of obtaining a leather-like sheet having a soft texture and excellent process passability.
　この場合においても、塗布された第２ホットメルト型湿分硬化ポリウレタン３の溶融又は軟化状態を調整するためにカレンダーロールＣＲとして、加熱型のカレンダーロールを用いてもよい。 In this case as well, a heating-type calender roll may be used as the calender roll CR in order to adjust the melting or softening state of the applied second hot-melt type moisture-curing polyurethane 3.
　そしてカレンダーロールＣＲにより溶融又は軟化状態の第２ホットメルト型湿分硬化ポリウレタン３の表面に基布４を貼り合わせることにより、皮革様シート１０が形成される。そして、得られた皮革様シート１０は、離型紙１で被覆された状態で巻き取りリール１３により巻き取られる。 And the leather-like sheet | seat 10 is formed by sticking the base fabric 4 on the surface of the 2nd hot-melt type moisture hardening polyurethane 3 of a molten or softened state with the calendar roll CR. Then, the obtained leather-like sheet 10 is taken up by the take-up reel 13 while being covered with the release paper 1.
　そして、巻き取られた皮革様シート１０を所定の時間養生することにより、第１ホットメルト型湿分硬化ポリウレタン２及び第２ホットメルト型湿分硬化ポリウレタン３の湿分硬化反応が進行し、ホットメルト型湿分硬化ポリウレタンが高分子量化される。 And the moisture hardening reaction of the 1st hot melt type moisture hardening polyurethane 2 and the 2nd hot melt type moisture hardening polyurethane 3 advances by curing the wound leather-like sheet 10 for a predetermined time, and hot The melt-type moisture-cured polyurethane has a high molecular weight.
　得られた皮革様シート１０の熟成条件としては、温度２０～４０℃、相対湿度５０～８０％の条件で、２０～５０時間程度熟成することが好ましい。このような熟成条件で熟成することにより、ホットメルト型湿分硬化ポリウレタンが湿分硬化及び湿分架橋する。これにより、機械的強度や耐水性に優れた皮革様シートが得られる。なお、皮革様シートは、表面に被覆された離型紙を剥離したものである。 The aging conditions of the obtained leather-like sheet 10 are preferably aging for about 20 to 50 hours at a temperature of 20 to 40 ° C. and a relative humidity of 50 to 80%. By aging under such aging conditions, the hot-melt type moisture-curing polyurethane is moisture-cured and moisture-crosslinked. Thereby, the leather-like sheet | seat excellent in mechanical strength and water resistance is obtained. In addition, a leather-like sheet | seat peels the release paper coat | covered on the surface.
　第１ホットメルト型湿分硬化ポリウレタンの塗布口と第２ホットメルト型湿分硬化ポリウレタンの塗布口の位置（例えば、図３に示す２つのナイフコーター２２ａと２３ａの距離）に関しては、塗布された前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布することができれば特に限定するものではないが、前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態を安定的に維持できる点で、１ｍ以内が好ましく、５０ｃｍ以内であることがより好ましい。 With respect to the position of the application port of the first hot melt type moisture curing polyurethane and the application port of the second hot melt type moisture curing polyurethane (for example, the distance between the two knife coaters 22a and 23a shown in FIG. 3) The first hot-melt type moisture-curing polyurethane is not particularly limited as long as the second hot-melt type moisture-curing polyurethane heated and melted can be applied to the surface in a melted or softened state. It is preferably within 1 m, and more preferably within 50 cm, in that the first hot-melt type moisture-cured polyurethane can stably maintain the melted or softened state.
　以上、説明したような工程においては、第１ホットメルト型湿分硬化ポリウレタン２が離型紙１表面に塗布された後、再固化する前に第２湿分硬化ポリウレタン３が加熱溶融状態で塗布される。従って、第１ホットメルト型湿分硬化ポリウレタン２から形成されるポリウレタン層と第２ホットメルト型湿分硬化ポリウレタン３から形成されるポリウレタン層との界面で互いに架橋し合い、界面における剥離強度が高くなる。また、溶融または軟化した状態の第１ホットメルト型湿分硬化ポリウレタン２は硬化反応が充分に進行していない。そのために、第１ホットメルト型湿分硬化ポリウレタン２と第２ホットメルト型湿分硬化ポリウレタン３とはそれらの界面において十分な架橋構造を形成し、またそれらの層の界面を不明瞭とすることができる。 In the process described above, after the first hot-melt type moisture-curing polyurethane 2 is applied to the surface of the release paper 1, the second moisture-curing polyurethane 3 is applied in a heated and melted state before re-solidifying. The Accordingly, the polyurethane layer formed from the first hot-melt type moisture-curing polyurethane 2 and the polyurethane layer formed from the second hot-melt type moisture-curing polyurethane 3 are cross-linked with each other, and the peel strength at the interface is high. Become. Further, the curing reaction of the first hot-melt type moisture-cured polyurethane 2 in a molten or softened state does not proceed sufficiently. Therefore, the first hot-melt type moisture-cure polyurethane 2 and the second hot-melt type moisture-cure polyurethane 3 form a sufficient cross-linked structure at their interface, and the interface of these layers is obscured. Can do.
　このような工程により得られた皮革様シート１０の断面模式図を図４に示す。 FIG. 4 shows a schematic cross-sectional view of the leather-like sheet 10 obtained by such a process.
　図４に示すように皮革様シート１０は、表面に被覆された離型紙１を剥離することにより完成する。このような皮革様シート１０においては、第１ホットメルト型湿分硬化ポリウレタン２から形成される第１ポリウレタン層と第２ホットメルト型湿分硬化ポリウレタン３から形成される第２ポリウレタン層との界面において架橋構造を形成しているために、第１ポリウレタン層と第２ポリウレタン層との接着力が充分に向上する。 As shown in FIG. 4, the leather-like sheet 10 is completed by peeling the release paper 1 coated on the surface. In such a leather-like sheet 10, the interface between the first polyurethane layer formed from the first hot-melt type moisture-curing polyurethane 2 and the second polyurethane layer formed from the second hot-melt type moisture-curing polyurethane 3. Since a cross-linked structure is formed in, the adhesive force between the first polyurethane layer and the second polyurethane layer is sufficiently improved.
　なお、本実施形態においては、送り出しリール１１から第１シートとして離型紙１を送り出し、送り出しリール１２から第２シートとして基布４を送り出したが、離型紙１の供給と基布４の供給する順を入れ替えて、送り出しリール１１から第１シートとして基布４を送り出し、送り出しリール１２から第２シートとして離型紙１を送り出してもよい。但し、この場合は使用するホットメルト型湿分硬化ポリウレタンの組み合わせを変更する必要がある。 In this embodiment, the release paper 1 is sent out as the first sheet from the delivery reel 11 and the base cloth 4 is sent out as the second sheet from the delivery reel 12. However, the supply of the release paper 1 and the supply of the base cloth 4 are performed. The base cloth 4 may be sent out as a first sheet from the delivery reel 11 and the release paper 1 may be sent out as a second sheet from the delivery reel 12 by changing the order. However, in this case, it is necessary to change the combination of the hot-melt type moisture-curing polyurethane used.
　以上、本発明に係る製造方法の一例を例示したが、本発明は上記のようなプロセスに限られるものではなく、皮革様シートの製造において、ホットメルト型湿分硬化ポリウレタンを基布または離型紙に塗布した後に、第１ホットメルト型湿分硬化ポリウレタンが溶融または軟化している状態で、加熱溶融状態の第２ホットメルト型湿分硬化ポリウレタンを塗布するようなプロセスに、特に限定なく適用しうる。 As mentioned above, although an example of the manufacturing method which concerns on this invention was illustrated, this invention is not restricted to the above processes, In manufacture of a leather-like sheet | seat, a hot melt type moisture hardening polyurethane is used as a base fabric or a release paper. After the coating, the first hot-melt type moisture-curing polyurethane is melted or softened, and the second hot-melt type moisture-curing polyurethane in a heat-melted state is applied without particular limitation. sell.
　このようにして得られた、皮革様シートは、第１ホットメルト型湿分硬化ポリウレタン２から形成される第１ポリウレタン層と第２ホットメルト型湿分硬化ポリウレタン３から形成される第２ポリウレタン層とが高い密着性を維持しうる。このために、得られる皮革様シートにおいては、折れ皺が細かく均一性のある外観性や風合いが向上する。 The leather-like sheet thus obtained has a first polyurethane layer formed from the first hot-melt type moisture-cure polyurethane 2 and a second polyurethane layer formed from the second hot-melt type moisture-cure polyurethane 3. Can maintain high adhesion. For this reason, in the obtained leather-like sheet, the appearance and texture with fine creases and uniform uniformity are improved.
　なお、得られた皮革様シートに対しては、さらに公知慣用の方法により、表面意匠性を付与するために、表層部を溶剤系、水系、エマルジョン系若しくは無溶剤系のポリウレタン樹脂やアクリル樹脂をコーティングしたり、あるいはバフィング加工やエンボス加工等の後加工を適宜行ってもよい。 In addition, for the obtained leather-like sheet, in order to impart surface designability by a known and conventional method, the surface layer portion is made of a solvent-based, water-based, emulsion-based or solvent-free polyurethane resin or acrylic resin. Coating or post-processing such as buffing or embossing may be appropriately performed.
　このようにして得られた皮革様シートは、履物、衣類、鞄、家具等の表面素材になる皮革様シートとして好ましく用いられうる。 The leather-like sheet thus obtained can be preferably used as a leather-like sheet that becomes a surface material for footwear, clothing, bags, furniture, and the like.
　以下に、本発明を実施例により具体的に説明するが、本発明は実施例に何ら限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the examples.
　はじめに、本実施例における溶融粘度の測定方法について説明する。 First, the method for measuring the melt viscosity in this example will be described.
　各ホットメルト型湿分硬化ポリウレタンの溶融粘度（ｍＰａ・ｓ）は、コーンプレート粘度計（ＩＣＩ社製）を用いて、コーンプレートの温度を所定の温度に設定して測定した。なお、第２塗布工程における第２ホットメルト型湿分硬化ポリウレタンの溶融粘度は、第２塗布工程の塗工温度（ナイフコーター温度）における第２ホットメルト型湿分硬化ポリウレタンの溶融粘度と定義した。さらに、第２塗布工程における第１ホットメルト型湿分硬化ポリウレタンの溶融粘度は、第２ホットメルト型湿分硬化ポリウレタンを塗布する直前の、塗布された第１ホットメルト型湿分硬化ポリウレタンの表面温度を測定し、その温度における溶融粘度とした。 The melt viscosity (mPa · s) of each hot-melt moisture-curing polyurethane was measured using a cone plate viscometer (manufactured by ICI) with the cone plate temperature set to a predetermined temperature. The melt viscosity of the second hot melt moisture-curing polyurethane in the second coating step was defined as the melt viscosity of the second hot melt moisture-curing polyurethane at the coating temperature (knife coater temperature) in the second coating step. . Furthermore, the melt viscosity of the first hot-melt type moisture-curing polyurethane in the second coating step is the surface of the applied first hot-melt type moisture-curing polyurethane immediately before the second hot-melt type moisture-curing polyurethane is applied. The temperature was measured and taken as the melt viscosity at that temperature.
　また、本実施例で用いた原材料を以下にまとめて説明する。 Also, the raw materials used in this example will be described together below.
　〈基布〉
平均繊度０．０７デシテックスの極細繊維からなる絡合不織布に水溶性ポリウレタン（ＤＩＣ（株）社製　ハイドランＷＬＳ６１２）を含浸した。厚さ１ｍｍ、目付け、５５０ｇ／ｍ２、比重０．５５ｇ／ｃｍ３の基布を得た。 <Base fabric>
A water-soluble polyurethane (Hydran WLS612 manufactured by DIC Corporation) was impregnated into an entangled nonwoven fabric made of ultrafine fibers having an average fineness of 0.07 dtex. A base fabric having a thickness of 1 mm, a basis weight of 550 g / m 2 , and a specific gravity of 0.55 g / cm 3 was obtained.
　〈ホットメルト型湿分硬化ポリウレタンＡ〉
タイフォース　ＥＸＰ－ＢＨ５０（ＤＩＣ（株）製のホットメルト型湿分硬化ポリウレタン）１００質量部、顔料（ＰＯＬＹＴＯＮ　ＰＵ－９３８２　ＢＬＡＣＫ、ＤＩＣ（株）製、以下同様）１５質量部を１２０℃で溶融混合した。これにより、１２０℃における溶融粘度が２７８０ｍＰａ・ｓであるホットメルト型湿分硬化ポリウレタンＡを得た。 <Hot melt type moisture curing polyurethane A>
100 parts by mass of Tyforth EXP-BH50 (hot melt type moisture-cured polyurethane manufactured by DIC Corporation) and 15 parts by mass of pigment (POLYTON PU-9382 BLACK, manufactured by DIC Corporation, the same applies hereinafter) at 120 ° C. did. As a result, a hot-melt type moisture-cured polyurethane A having a melt viscosity at 120 ° C. of 2780 mPa · s was obtained.
　〈ホットメルト型湿分硬化ポリウレタンＢ〉
タイフォースＫＭＭ－１００（ＤＩＣ（株）製のホットメルト型湿分硬化ポリウレタン）１００質量部、顔料１５質量部を１２５℃で溶融混合した。これにより、１２０℃における溶融粘度が３２００ｍＰａ・ｓであるホットメルト型湿分硬化ポリウレタンＢを得た。 <Hot melt type moisture curing polyurethane B>
100 parts by mass of Tyforce KMM-100 (hot melt type moisture-cured polyurethane manufactured by DIC Corporation) and 15 parts by mass of pigment were melt-mixed at 125 ° C. As a result, a hot melt moisture-cured polyurethane B having a melt viscosity at 120 ° C. of 3200 mPa · s was obtained.
　〈ホットメルト型湿分硬化ポリウレタンＣ〉
タイフォースＫＭＭ－１００（ＤＩＣ（株）製のホットメルト型湿分硬化ポリウレタン）１００質量部、顔料１５質量部、発泡剤２質量部を１３５℃で溶融混合した。これにより、１２０℃における溶融粘度が３２００ｍＰａ・ｓである発泡型のホットメルト型湿分硬化ポリウレタン３を得た。なお、発泡剤としては、エチレングリコール（ＥＧ）／水／ＰＯＬＹＣＡＴ－８［エアープロダクツジャパン社製、Ｎ，Ｎ－ジメチルシクロヘキシルアミン（ＤＭＣＨＡ）］＝０．５／０．０５／０．１（質量部）の組成物を用いた。 <Hot melt type moisture curing polyurethane C>
100 parts by mass of Tyforce KMM-100 (hot melt type moisture-cured polyurethane manufactured by DIC Corporation), 15 parts by mass of pigment, and 2 parts by mass of a foaming agent were melt-mixed at 135 ° C. As a result, a foamed hot-melt moisture-curing polyurethane 3 having a melt viscosity at 120 ° C. of 3200 mPa · s was obtained. As the blowing agent, ethylene glycol (EG) / water / POLYCAT-8 [manufactured by Air Products Japan, N, N-dimethylcyclohexylamine (DMCHA)] = 0.5 / 0.05 / 0.1 (mass) Part) composition.
　〈離型紙〉
　リンテック（株）製のシボ入り離型紙　Ｒ－８ <Release paper>
Release paper R-8 with wrinkles made by Lintec Corporation
　［実施例１］
　図２に示したような製造プロセスを用いて皮革様シートを製造した。 [Example 1]
A leather-like sheet was manufactured using a manufacturing process as shown in FIG.
　具体的には、はじめに送り出しリール１１から第１シートとして離型紙１を１ｍ／分の速度で連続して送り出し、矢印方向に回転する主ロールＲにより搬送し、巻き取りリール１３により巻き取ってラインを形成した。このとき主ロールＲの表面温度は５０℃になるように制御した。そして、ライン上の離型紙に向けて、第１ホットメルト型湿分硬化ポリウレタン２として樹脂フィーダー２ｂ中に収容されたホットメルト型湿分硬化ポリウレタンＡを１１０℃で溶融した状態で流下し、ナイフコーター２ａにより離型紙１表面に均一な厚みで塗布した（第１塗布工程）。なお、ナイフコーター２ａの表面温度は図略のヒーターにより１１０℃に制御した。このときナイフコーター２ａと離型紙とのギャップを５０μｍに調整していた。 Specifically, first, the release paper 1 is continuously fed out from the feed reel 11 as a first sheet at a speed of 1 m / min, conveyed by the main roll R rotating in the direction of the arrow, and taken up by the take-up reel 13 to form a line. Formed. At this time, the surface temperature of the main roll R was controlled to be 50 ° C. Then, toward the release paper on the line, the hot melt type moisture curing polyurethane A accommodated in the resin feeder 2b as the first hot melt type moisture curing polyurethane 2 flows down in a state melted at 110 ° C. The coater 2a was applied to the surface of the release paper 1 with a uniform thickness (first application step). The surface temperature of the knife coater 2a was controlled at 110 ° C. with a heater (not shown). At this time, the gap between the knife coater 2a and the release paper was adjusted to 50 μm.
　次に、離型紙１表面に塗布されたホットメルト型湿分硬化ポリウレタンＡが溶融している状態でその表面に第２ホットメルト型湿分硬化ポリウレタン３として、１３５℃で溶融させたホットメルト型湿分硬化ポリウレタンＣを塗布した（第２塗布工程）。このときロールコーター３ａの表面温度は図略のヒーターにより１３５℃になるように制御されていた。このときロールコーター３ａと離型紙とのギャップは２５０μｍになるように調整した。この第２塗布工程においては、塗布されたホットメルト型湿分硬化ポリウレタンＡの表面温度は約１２０℃であり、そのときの溶融粘度は約５０００ｍＰａ・ｓであった。また、ホットメルト型湿分硬化ポリウレタンＣの１３５℃に於ける溶融粘度は約２５００ｍＰａ・ｓであった。従って、第２塗布工程における、ホットメルト型湿分硬化ポリウレタンＡの溶融粘度は、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度の約２倍程度であった。 Next, the hot melt type moisture cured polyurethane A applied to the surface of the release paper 1 is melted at 135 ° C. as the second hot melt type moisture cured polyurethane 3 on the surface thereof. Moisture-cure polyurethane C was applied (second application step). At this time, the surface temperature of the roll coater 3a was controlled to 135 ° C. by a heater (not shown). At this time, the gap between the roll coater 3a and the release paper was adjusted to 250 μm. In this second coating step, the surface temperature of the applied hot melt moisture-curing polyurethane A was about 120 ° C., and the melt viscosity at that time was about 5000 mPa · s. Further, the melt viscosity at 135 ° C. of the hot-melt type moisture-cure polyurethane C was about 2500 mPa · s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about twice the melt viscosity of the hot melt moisture-curing polyurethane C.
　次に、塗布されたホットメルト型湿分硬化ポリウレタンＣが溶融している状態でその表面に第２シートである基布４を貼り合せた（貼合工程）。具体的には、送り出しリール１２から基布４を送り出し、ホットメルト型湿分硬化ポリウレタンＣが溶融している状態でカレンダーロールＣＲにより貼り合わせた。なお、カレンダーロールＣＲの表面温度は図略のヒーターにより５０℃に制御されていた。このようにして、図４に示したような層構造を有する皮革様シート１０が形成された。そして、得られた皮革様シートは、離型紙で被覆された状態で巻き取りリール１３により巻き取られた。 Next, the base fabric 4 as the second sheet was bonded to the surface of the applied hot-melt type moisture-cure polyurethane C in a molten state (bonding step). Specifically, the base fabric 4 was sent out from the delivery reel 12 and bonded with a calendar roll CR in a state where the hot-melt moisture-cure polyurethane C was melted. The surface temperature of the calendar roll CR was controlled at 50 ° C. by a heater (not shown). In this way, a leather-like sheet 10 having a layer structure as shown in FIG. 4 was formed. Then, the obtained leather-like sheet was wound up by the take-up reel 13 while being covered with a release paper.
　そして、巻き取られた状態で、皮革様シート１０を温度４０℃、相対湿度６０％の条件で３５時間熟成した。熟成後、得られた皮革様シート１０を所定の面積だけ切断し、離型紙を剥離して以下の方法により層間接着性を評価した。 Then, in a wound state, the leather-like sheet 10 was aged for 35 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 60%. After aging, the obtained leather-like sheet 10 was cut by a predetermined area, the release paper was peeled off, and interlayer adhesion was evaluated by the following method.
　（層間接着性）
　離型紙が剥離された皮革様シートの第２ポリウレタン層の表面に、布ホットメルトテープ〔商標：メルコテープ、サン化成（株）製〕を１３０℃で５秒間熱圧着した後、２００ｍｍ／分のヘッドスピードにて、ＪＩＳ
Ｋ６８５４－２に準拠してテンシロン（島津製作所製）を用いて剥離強さを測定した。また、そのときの剥離した部分の位置を確認した。 (Interlayer adhesion)
A cloth hot melt tape (trademark: Melco Tape, manufactured by Sun Kasei Co., Ltd.) was thermocompression bonded at 130 ° C. for 5 seconds to the surface of the second polyurethane layer of the leather-like sheet from which the release paper was peeled, and then 200 mm / min. JIS at head speed
The peel strength was measured using Tensilon (manufactured by Shimadzu Corporation) in accordance with K6854-2. Moreover, the position of the part which peeled at that time was confirmed.
　その結果、得られた皮革様シートの剥離強さは、１１．０ｋｇ／２５ｍｍであり、基布４層内で内部剥離していた。 As a result, the peel strength of the obtained leather-like sheet was 11.0 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric.
　［実施例２］
　塗布機構が異なる、図３に示したような製造プロセスを用い、さらに、第１ホットメルト型湿分硬化ポリウレタン２として、ホットメルト型湿分硬化ポリウレタンＢを用いた以外は実施例１と同様にして皮革様シートを製造した。 [Example 2]
The manufacturing process as shown in FIG. 3 with different application mechanisms was used, and the hot-melt moisture-cure polyurethane B was used as the first hot-melt moisture-cure polyurethane 2. A leather-like sheet was manufactured.
　具体的には、図３に示すように、２つのナイフコーター２２ａ，２３ａとホットメルト型湿分硬化ポリウレタンを収納する２つの樹脂供給部２２ｂ，２３ｂを備える一体化された塗布機構２５を用いた。そして、樹脂供給部２２ｂに第１ホットメルト型湿分硬化ポリウレタン２として、ホットメルト型湿分硬化ポリウレタンＢを収納し、樹脂供給部２３ｂに第２ホットメルト型湿分硬化ポリウレタン３として、ホットメルト型湿分硬化ポリウレタンＣを収納した。 Specifically, as shown in FIG. 3, an integrated coating mechanism 25 including two knife coaters 22a and 23a and two resin supply portions 22b and 23b for storing hot-melt type moisture-cure polyurethane is used. . The resin supply unit 22b stores hot melt type moisture curing polyurethane B as the first hot melt type moisture curing polyurethane 2, and the resin supply unit 23b stores the second hot melt type moisture curing polyurethane 3 as the hot melt type moisture curing polyurethane 3. Mold moisture cured polyurethane C was housed.
　そして、送り出しリール１１から第１シートとして離型紙１を１ｍ／分の速度で連続して送り出し、矢印方向に回転する主ロールＲにより搬送し、巻き取りリール１３により巻き取ってラインを形成した。このとき主ロールＲの表面温度は５０℃になるように制御した。そして、ライン上の離型紙１に向けて、樹脂供給部２２ｂ中に収容されたホットメルト型湿分硬化ポリウレタンＢを溶融した状態で流下し、ナイフコーター２２ａにより離型紙１表面に均一な厚みで塗布した（第１塗布工程）。その直後に、樹脂供給部２３ｂ中に収容されたホットメルト型湿分硬化ポリウレタンＣを溶融した状態で流下し、ナイフコーター２３ａにより均一な厚みで塗布した（第２塗布工程）。なお、ナイフコーター２２ａと離型紙表面とのギャップは５０μｍ、ナイフコーター２３ａと離型紙表面とのギャップは２５０μｍに調整していた。ナイフコーター２２ａ及び樹脂供給部２２ｂは１１０℃に制御されており，ナイフコーター２３ａ及び樹脂供給部２３ｂは１２０℃に制御されていた。第２塗布工程においては、第１塗布工程で塗布されたホットメルト型湿分硬化ポリウレタンＢの表面温度は約１１０℃であり、そのときの溶融粘度は約５０００ｍＰａ・ｓであった。また、ホットメルト型湿分硬化ポリウレタンＣの１２０℃における溶融粘度は約３２００ｍＰａ・ｓであった。従って、第２塗布工程における、ホットメルト型湿分硬化ポリウレタンＢの溶融粘度は、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度の約１．６倍程度であった。 Then, the release paper 1 was continuously sent out from the delivery reel 11 as a first sheet at a speed of 1 m / min, conveyed by the main roll R rotating in the direction of the arrow, and taken up by the take-up reel 13 to form a line. At this time, the surface temperature of the main roll R was controlled to be 50 ° C. Then, the hot melt moisture-curing polyurethane B accommodated in the resin supply unit 22b flows down toward the release paper 1 on the line in a melted state, and the knife coater 22a has a uniform thickness on the surface of the release paper 1 It applied (first application process). Immediately after that, the hot-melt type moisture-cure polyurethane C accommodated in the resin supply unit 23b was flowed down in a molten state and applied with a uniform thickness by the knife coater 23a (second application step). The gap between the knife coater 22a and the release paper surface was adjusted to 50 μm, and the gap between the knife coater 23a and the release paper surface was adjusted to 250 μm. The knife coater 22a and the resin supply unit 22b were controlled at 110 ° C., and the knife coater 23a and the resin supply unit 23b were controlled at 120 ° C. In the second application step, the surface temperature of the hot-melt type moisture-cured polyurethane B applied in the first application step was about 110 ° C., and the melt viscosity at that time was about 5000 mPa · s. Further, the melt viscosity at 120 ° C. of the hot-melt type moisture-cure polyurethane C was about 3200 mPa · s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane B in the second coating step was about 1.6 times the melt viscosity of the hot melt moisture-curing polyurethane C.
　以降の工程は実施例１と同様にして皮革様シートを製造した。その結果、得られた皮革様シートの剥離強さは、１０．２ｋｇ／２５ｍｍであり、基布４層内で内部剥離していた。 The subsequent steps were performed in the same manner as in Example 1 to produce a leather-like sheet. As a result, the peel strength of the obtained leather-like sheet was 10.2 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric.
　［実施例３］
第１塗布工程において、ホットメルト型湿分硬化ポリウレタンＡを１００℃で溶融した状態で流下し、第２塗布工程において、ホットメルト型湿分硬化ポリウレタンＣを１４０℃で溶融した状態で流下した以外は実施例１と同様にして皮革様シートを製造した。このときロールコーター３ａの表面温度は図略のヒーターにより１４０℃になるように制御されていた。このとき、第２塗布工程においては、第１塗布工程で塗布されたホットメルト型湿分硬化ポリウレタンＡの溶融粘度は約６５００ｍＰａ・ｓになっており、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度は約１８００ｍＰａ・ｓであった。従って、第２塗布工程における、ホットメルト型湿分硬化ポリウレタンＡの溶融粘度は、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度の約３．６倍程度であった。得られた皮革様シートの剥離強さの測定においては、主として基布４層内で内部剥離し、若干、ポリウレタン層同士の界面でも剥離が見られたが、剥離強さは１０．１ｋｇ／２５ｍｍと高いものであった。 [Example 3]
In the first coating step, the hot-melt type moisture-curing polyurethane A is flowed down in a melted state at 100 ° C., and in the second coating step, the hot-melt type moisture-curing polyurethane C is flowed down in a melted state at 140 ° C. Produced a leather-like sheet in the same manner as in Example 1. At this time, the surface temperature of the roll coater 3a was controlled to 140 ° C. by a heater (not shown). At this time, in the second coating step, the melt viscosity of the hot-melt type moisture-cured polyurethane A applied in the first coating step is about 6500 mPa · s, and the melt viscosity of the hot-melt type moisture-cured polyurethane C is about 6500 mPa · s. Was about 1800 mPa · s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about 3.6 times the melt viscosity of the hot melt moisture-curing polyurethane C. In the measurement of peel strength of the obtained leather-like sheet, internal peeling mainly occurred in the four layers of the base fabric, and some peeling was observed even at the interface between the polyurethane layers, but the peeling strength was 10.1 kg / 25 mm. It was expensive.
　［実施例４］
第１塗布工程において、ホットメルト型湿分硬化ポリウレタンＡを１２０℃で溶融した状態で流下し、第２塗布工程において、ホットメルト型湿分硬化ポリウレタンＣを１１５℃で溶融した状態で流下した以外は実施例１と同様にして皮革様シートを製造した。このときロールコーター３ａの表面温度は図略のヒーターにより１１５℃になるように制御されていた。このとき、第２塗布工程においては、第１塗布工程で塗布されたホットメルト型湿分硬化ポリウレタンＡの溶融粘度は約２７００ｍＰａ・ｓになっており、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度は約４０００ｍＰａ・ｓであった。従って、第２塗布工程における、ホットメルト型湿分硬化ポリウレタンＡの溶融粘度は、ホットメルト型湿分硬化ポリウレタンＣの溶融粘度の約０．７倍程度であった。得られた皮革様シートの剥離強さは、１０．６ｋｇ／２５ｍｍであり、基布４層内で内部剥離していた。なお、ホットメルト型湿分硬化ポリウレタンＡから形成されたポリウレタン層とホットメルト型湿分硬化ポリウレタンＣ形成されたポリウレタン層とは部分的に混ざり合っている部分が存在した。 [Example 4]
In the first coating step, the hot-melt type moisture-curing polyurethane A flows down in a state melted at 120 ° C., and in the second coating step, the hot-melt type moisture-curing polyurethane C flows down in a state melted at 115 ° C. Produced a leather-like sheet in the same manner as in Example 1. At this time, the surface temperature of the roll coater 3a was controlled to 115 ° C. by a heater (not shown). At this time, in the second coating step, the melt viscosity of the hot-melt type moisture-cured polyurethane A applied in the first coating step is about 2700 mPa · s, and the melt viscosity of the hot-melt type moisture-cured polyurethane C is about 2700 mPa · s. Was about 4000 mPa · s. Therefore, the melt viscosity of the hot melt moisture-curing polyurethane A in the second coating step was about 0.7 times the melt viscosity of the hot melt moisture-curing polyurethane C. The peel strength of the obtained leather-like sheet was 10.6 kg / 25 mm, and internal peeling occurred within the four layers of the base fabric. In addition, the polyurethane layer formed from the hot-melt type moisture-curing polyurethane A and the polyurethane layer formed from the hot-melt type moisture-curing polyurethane C were partially mixed.
　［比較例１］
　図１に示したようなプロセスを用いて皮革様シートを製造した。 [Comparative Example 1]
A leather-like sheet was produced using a process as shown in FIG.
　具体的には、図１に示すように、送り出しリール３０から巻き取りリール３８に向けて離型紙１を１ｍ／分の速度で送り出してラインを形成した。そして、送り出しリール３０に巻かれた離型紙１を、ローラー３１、３２に乗せて搬送した。そして、ナイフコーター３０３で剥離紙表面に第１ホットメルト型湿分硬化ポリウレタン３１２として、１２０℃で加熱溶融させたホットメルト型湿分硬化ポリウレタンＡを塗布することにより皮膜層を形成した。このとき塗布厚を５０μｍになるように調整した。続いて、ホットメルト型湿分硬化ポリウレタンＡからなる皮膜層表面に、水蒸気噴霧器３０４で水蒸気を吹きつけた。そして、ローラー３３ａ，３３ｂに乗せてローラー３４に送りこみ、ナイフコーター３０５で第２ホットメルト型湿分硬化ポリウレタン３１３として、１２０℃で加熱溶融させたホットメルト型湿分硬化ポリウレタンＣを塗布厚を２００μｍになるように調整して塗布した。そして、送り出しリール３６から基布３７を供給し、ローラー３５でホットメルト型湿分硬化ポリウレタンＣに基布を貼り合わせて皮革様シートを製造した。 Specifically, as shown in FIG. 1, the release paper 1 was fed from the feed reel 30 toward the take-up reel 38 at a speed of 1 m / min to form a line. Then, the release paper 1 wound around the delivery reel 30 was carried on rollers 31 and 32. And the coating layer was formed by apply | coating the hot melt type moisture hardening polyurethane A heat-melted at 120 degreeC as the 1st hot melt type moisture hardening polyurethane 312 with the knife coater 303 on the release paper surface. At this time, the coating thickness was adjusted to 50 μm. Subsequently, water vapor was sprayed onto the surface of the film layer made of hot-melt type moisture-curing polyurethane A with a water vapor sprayer 304. Then, it is placed on rollers 33a and 33b and fed to roller 34, and hot melt type moisture curing polyurethane C heated and melted at 120 ° C. as second hot melt type moisture curing polyurethane 313 by knife coater 305 is applied to a thickness. The coating was adjusted to 200 μm. And the base fabric 37 was supplied from the delivery reel 36, and the base fabric was bonded together with the hot-melt type moisture hardening polyurethane C with the roller 35, and the leather-like sheet | seat was manufactured.
　上記工程においては、第１ホットメルト型湿分硬化ポリウレタン２が表面にタックが部分的に残っていた。そのために、図１に示すローラー３３ａ，３３ｂに対して積層中間体が巻きつき、工程通過性に問題が生じた。 In the above process, the first hot-melt type moisture-curing polyurethane 2 was partially left on the surface. Therefore, the laminated intermediate body is wound around the rollers 33a and 33b shown in FIG.
［比較例２］
　離型紙１を１．０ｍ／分の速度で送り出すかわりに、０．５ｍ／分の速度で送り出すことにより、ライン速度を低下させた以外は比較例１と同様にして皮革様シートを製造し、評価した、ライン速度を低下させたことにより、表面タック性はある程度抑制され、連続生産性も改善された。 [Comparative Example 2]
Instead of sending the release paper 1 at a speed of 1.0 m / min, a leather-like sheet was produced in the same manner as in Comparative Example 1 except that the line speed was lowered by sending it at a speed of 0.5 m / min. By reducing the evaluated line speed, the surface tack was suppressed to some extent and the continuous productivity was also improved.
　得られた皮革様シートを温度４０℃、相対湿度６０％の条件で３５時間熟成した。そして熟成後、得られた皮革様シートを所定の面積だけ切断し、離型紙を剥離して実施例１と同様の方法により層間接着性を評価した。その結果、皮革様シートの剥離強さは６．５ｋｇ／２５ｍｍであり、ホットメルト型湿分硬化ポリウレタンＡからなる層とホットメルト型湿分硬化ポリウレタンＢからなる層との界面で界面剥離していた。 The obtained leather-like sheet was aged for 35 hours under conditions of a temperature of 40 ° C. and a relative humidity of 60%. Then, after aging, the obtained leather-like sheet was cut by a predetermined area, the release paper was peeled off, and the interlayer adhesion was evaluated by the same method as in Example 1. As a result, the peel strength of the leather-like sheet was 6.5 kg / 25 mm, and interface peeling occurred at the interface between the layer made of hot-melt type moisture-curing polyurethane A and the layer made of hot-melt type moisture-curing polyurethane B. It was.
　以上の実施例の結果が示すように、本願発明に係る実施例１～４で得られた皮革様シートは何れも剥離強さが高かった。また、実施例１～２、４においては、ポリウレタン層同士の界面では全く剥離が見られなかった。これは、２種のホットメルト型湿分硬化ポリウレタンが溶融状態で積層されることにより、界面が不明瞭になり、また、界面において架橋構造が充分に形成されるためであると思われる。なお、実施例３においては、ホットメルト型湿分硬化ポリウレタンＡから形成されたポリウレタン層とホットメルト型湿分硬化ポリウレタンＣから形成されたポリウレタン層との界面においても、部分的に若干の剥離は見られたが、剥離強さは充分に高いものであった。 As shown in the results of the above Examples, the leather-like sheets obtained in Examples 1 to 4 according to the present invention all had high peel strength. In Examples 1 to 2, and 4, no peeling was observed at the interface between the polyurethane layers. This is probably because the two types of hot-melt type moisture-cured polyurethane are laminated in a molten state, so that the interface becomes unclear and a sufficient crosslinked structure is formed at the interface. In Example 3, some peeling was partially also at the interface between the polyurethane layer formed from the hot-melt type moisture-curing polyurethane A and the polyurethane layer formed from the hot-melt type moisture-curing polyurethane C. Although seen, the peel strength was sufficiently high.
　一方、比較例１のように、ホットメルト型湿分硬化ポリウレタンＡを塗布して、再固化させたときにタックが残っている場合には工程通過性がわるく、連続生産が困難であった。また、比較例２のように、ホットメルト型湿分硬化ポリウレタンＡを塗布して、タックがなくなる程度に固化するような低速のラインで生産した場合には、剥離強さが著しく低かった。これは、２つのポリウレタン層における界面が明確になり、また、２つの層間に充分な架橋構造が形成されなかったためであると思われる。 On the other hand, as in Comparative Example 1, when the hot-melt type moisture-curing polyurethane A was applied and re-solidified, the tackiness remained and the continuous production was difficult. Further, as in Comparative Example 2, when the hot melt moisture-curing polyurethane A was applied and produced on a low-speed line that solidified to such an extent that tack was eliminated, the peel strength was remarkably low. This is presumably because the interface between the two polyurethane layers became clear and a sufficient crosslinked structure was not formed between the two layers.
　以上説明されたように、本発明の一局面は、加熱溶融させた第１ホットメルト型湿分硬化ポリウレタンを第１シートの表面に塗布する第１塗布工程と、塗布された前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布する第２塗布工程と、塗布された前記第２ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に第２シートを貼り合せる貼合工程とを備える、皮革様シートの製造方法である。 As described above, according to one aspect of the present invention, the first hot-melt type moisture-cured polyurethane heated and melted is applied to the surface of the first sheet, and the first hot-melt applied A second application step of applying a second hot-melt type moisture-curing polyurethane heated and melted on the surface of the mold-moisture-curing polyurethane in a melted or softened state, and the applied second hot-melt type moisture It is a manufacturing method of a leather-like sheet provided with the pasting process of pasting the 2nd sheet on the surface in the state where hardened polyurethane has melted or softened.
　このような製造方法によれば、第１ホットメルト型湿分硬化ポリウレタンと第２ホットメルト型湿分硬化ポリウレタンとが互いに架橋しあった界面が形成されることで、界面における剥離強度が高くなる。さらには前述した従来の製造方法から形成される明確な界面を形成させ難くすることで界面が不明瞭になり、界面における剥離強度がより高くなる。また、溶融または軟化した状態の第１ホットメルト型湿分硬化ポリウレタンは硬化反応が十分に進行する前に前記第２ホットメルト型湿分硬化ポリウレタンが塗布されるために、前記第１ホットメルト型湿分硬化ポリウレタンが形成する層と前記第２ホットメルト型湿分硬化ポリウレタンが形成する層との間に充分な架橋構造を形成することができる。さらに、連続生産する際には、第１ホットメルト型湿分硬化ポリウレタンからなる層及び第２ホットメルト型湿分硬化ポリウレタンからなる層は、表面がそれぞれ第１シート及び第２シートで被覆されているために、未硬化のホットメルト型湿分硬化ポリウレタンに由来するタックが表れない。そのために、工程通過性にも優れる。 According to such a manufacturing method, the peel strength at the interface is increased by forming an interface in which the first hot-melt type moisture-cured polyurethane and the second hot-melt type moisture-cured polyurethane are cross-linked with each other. . Further, by making it difficult to form a clear interface formed by the above-described conventional manufacturing method, the interface becomes unclear and the peel strength at the interface becomes higher. In addition, the first hot-melt type moisture-cured polyurethane in the melted or softened state is coated with the second hot-melt type moisture-cured polyurethane before the curing reaction sufficiently proceeds. A sufficient cross-linked structure can be formed between the layer formed by the moisture-cured polyurethane and the layer formed by the second hot-melt type moisture-cured polyurethane. Further, in the case of continuous production, the surface of the layer made of the first hot-melt type moisture-curing polyurethane and the layer made of the second hot-melt type moisture-curing polyurethane are coated with the first sheet and the second sheet, respectively. Therefore, tack derived from uncured hot melt moisture-cured polyurethane does not appear. Therefore, the process passability is also excellent.
　また、前記第２塗布工程においては、前記第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が前記第２ホットメルト型湿分硬化ポリウレタンの溶融粘度よりも高いこと、さらには、前記第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が前記第２ホットメルト型湿分硬化ポリウレタンの溶融粘度の１．５～２倍であることが好ましい。第２ホットメルト型湿分硬化ポリウレタンを塗布する際の第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が低すぎる場合には、先に塗布された第１ホットメルト型湿分硬化ポリウレタン層と新たに塗布された第２ホットメルト型湿分硬化ポリウレタンとが混ざってしまい、各層ごとの特性を充分に維持できなくなる傾向がある。 In the second application step, the melt viscosity of the first hot melt moisture-curing polyurethane is higher than the melt viscosity of the second hot melt moisture-curing polyurethane, and further, the first hot melt The melt viscosity of the moisture-curing polyurethane is preferably 1.5 to 2 times the melt viscosity of the second hot-melt moisture-curing polyurethane. If the melt viscosity of the first hot-melt type moisture-cure polyurethane when applying the second hot-melt type moisture-cure polyurethane is too low, the first hot-melt type moisture-cure polyurethane layer previously applied and a new one The second hot-melt moisture-cured polyurethane applied to the mixture tends to be mixed, and the characteristics of each layer cannot be sufficiently maintained.
　また、前記第１ホットメルト型湿分硬化ポリウレタン及び／または前記第２ホットメルト型湿分硬化ポリウレタンが発泡剤を含有する場合には、中間層として用いられるような弾性を有するポリウレタン層を容易に形成することができる。 Further, when the first hot-melt type moisture-curing polyurethane and / or the second hot-melt type moisture-curing polyurethane contains a foaming agent, an elastic polyurethane layer used as an intermediate layer can be easily formed. Can be formed.
　また、上記何れかの製造方法により得られた皮革様シートは、第１ホットメルト型湿分硬化ポリウレタンから形成される第１ポリウレタン層と第２ホットメルト型湿分硬化ポリウレタンから形成される第２ポリウレタン層とが高い密着性と一体感を維持しうる。このために、得られる皮革様シートは折れ皺が細かく、均一性のある外観性や風合い等に優れている。 In addition, the leather-like sheet obtained by any one of the above production methods is a second polyurethane layer formed from the first polyurethane layer formed from the first hot melt type moisture cured polyurethane and the second hot melt type moisture cured polyurethane. The polyurethane layer can maintain high adhesion and unity. For this reason, the obtained leather-like sheet has fine creases and is excellent in uniform appearance and texture.
　本発明によれば、ホットメルト型湿分硬化ポリウレタンから形成される２層のポリウレタン積層部分の界面の剥離強度を充分に高めることができる、皮革様シートの製造方法が提供される。 According to the present invention, there is provided a method for producing a leather-like sheet that can sufficiently enhance the peel strength at the interface between two polyurethane laminates formed from hot-melt moisture-cured polyurethane.

Claims (6)

  1. 　加熱溶融させた第１ホットメルト型湿分硬化ポリウレタンを第１シートの表面に塗布する第１塗布工程と、塗布された前記第１ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に加熱溶融させた第２ホットメルト型湿分硬化ポリウレタンを塗布する第２塗布工程と、塗布された前記第２ホットメルト型湿分硬化ポリウレタンが溶融又は軟化している状態でその表面に第２シートを貼り合せる貼合工程とを備えることを特徴とする皮革様シートの製造方法。 In a state where the first hot-melt type moisture-cure polyurethane that has been heated and melted is applied to the surface of the first sheet, and the applied first hot-melt type moisture-cure polyurethane is melted or softened A second application step of applying a second hot-melt type moisture-curing polyurethane heated and melted on the surface, and the applied second hot-melt type moisture-cure polyurethane on the surface in a melted or softened state; The manufacturing method of the leather-like sheet | seat characterized by including the bonding process which bonds a 2nd sheet | seat.
  2. 　前記第１シート及び前記第２シートの何れか一方が、基布または既にポリウレタン層が形成された基布であり、他の一方が、離型紙または既にポリウレタン層が形成された離型紙である請求項１に記載の皮革様シートの製造方法。 Either one of the first sheet and the second sheet is a base fabric or a base fabric on which a polyurethane layer has already been formed, and the other is a release paper or a release paper on which a polyurethane layer has already been formed. Item 2. A method for producing a leather-like sheet according to Item 1.
  3. 　前記第２塗布工程において、前記第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が前記第２ホットメルト型湿分硬化ポリウレタンの溶融粘度よりも高い請求項１または２に記載の皮革様シートの製造方法。 The leather-like sheet according to claim 1 or 2, wherein in the second application step, the melt viscosity of the first hot-melt type moisture-cured polyurethane is higher than the melt viscosity of the second hot-melt type moisture-cured polyurethane. Method.
  4. 　前記第２塗布工程において、前記第１ホットメルト型湿分硬化ポリウレタンの溶融粘度が前記第２ホットメルト型湿分硬化ポリウレタンの溶融粘度の１．５～２倍の範囲である請求項３に記載の皮革様シートの製造方法。 The melt viscosity of the first hot-melt type moisture-cure polyurethane in the second application step is in a range of 1.5 to 2 times the melt viscosity of the second hot-melt type moisture-cure polyurethane. Method of leather-like sheet.
  5. 　前記第１ホットメルト型湿分硬化ポリウレタン及び／または前記第２ホットメルト型湿分硬化ポリウレタンが発泡剤を含有する請求項１～４の何れか１項に記載の皮革様シートの製造方法。 The method for producing a leather-like sheet according to any one of claims 1 to 4, wherein the first hot-melt type moisture-curing polyurethane and / or the second hot-melt type moisture-curing polyurethane contains a foaming agent.
  6. 　請求項１～５の何れか１項に記載された皮革様シートの製造方法により得られた皮革様シート。 A leather-like sheet obtained by the method for producing a leather-like sheet according to any one of claims 1 to 5.
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JP6485726B1 (en) * 2017-09-25 2019-03-20 Dic株式会社 Synthetic leather manufacturing method
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