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WO2013141207A1 - 被覆ポリウレタンフォームの製造方法、被覆ポリウレタンフォーム、衣料材料、ブラジャーのパッド、および、ブラジャーのカップ - Google Patents

被覆ポリウレタンフォームの製造方法、被覆ポリウレタンフォーム、衣料材料、ブラジャーのパッド、および、ブラジャーのカップ Download PDF

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Publication number
WO2013141207A1
WO2013141207A1 PCT/JP2013/057663 JP2013057663W WO2013141207A1 WO 2013141207 A1 WO2013141207 A1 WO 2013141207A1 JP 2013057663 W JP2013057663 W JP 2013057663W WO 2013141207 A1 WO2013141207 A1 WO 2013141207A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane foam
coating layer
polyisocyanate
molecular weight
raw material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2013/057663
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English (en)
French (fr)
Japanese (ja)
Inventor
大介 西口
正和 景岡
山崎　聡
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Filing date
Publication date
Application filed by Mitsui Chemicals Inc filed Critical Mitsui Chemicals Inc
Priority to JP2014506227A priority Critical patent/JP5832633B2/ja
Publication of WO2013141207A1 publication Critical patent/WO2013141207A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/245—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it being a foam layer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4866—Polyethers having a low unsaturation value
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41C—CORSETS; BRASSIERES
    • A41C3/00—Brassieres
    • A41C3/12—Component parts
    • A41C3/14—Stiffening or bust-forming inserts
    • A41C3/144—Pads
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric 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
    • B32B2307/10—Properties of the layers or laminate having particular acoustical properties
    • 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
    • B32B2307/56—Damping, energy absorption
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2457/00—Electrical equipment
    • 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
    • B32B2605/00—Vehicles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0008—Foam properties flexible
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2150/00—Compositions for coatings
    • C08G2150/60—Compositions for foaming; Foamed or intumescent coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2350/00—Acoustic or vibration damping material

Definitions

  • the present invention relates to a method for producing a coated polyurethane foam, a coated polyurethane foam produced by the production method, a clothing material formed from the coated polyurethane foam, a pad of a brassiere formed from the clothing material, and a pad of the brassiere A brassiere cup comprising:
  • Aromatic polyurethane foam used for clothing pads and the like may be discolored by exposure to ultraviolet rays or oxidizing gas (nitrogen oxide gas (NOx), etc.).
  • oxidizing gas nitrogen oxide gas (NOx), etc.
  • a general-purpose flexible polyurethane foam obtained by reacting tolylene diisocyanate and a polyol, aliphatic isocyanate, alicyclic isocyanate for example, one side of a general-purpose flexible polyurethane foam obtained by reacting tolylene diisocyanate and a polyol, aliphatic isocyanate, alicyclic isocyanate
  • a non-yellowing flexible polyurethane foam sheet obtained by reacting an aromatic isocyanate that does not have an isocyanate group directly on the aromatic ring and a polyol is laminated using an adhesive and is integrally formed.
  • the general-purpose flexible polyurethane foam and the non-yellowing flexible polyurethane foam must be foam-molded in advance, and then bonded to each other with an adhesive, which makes the process complicated.
  • an object of the present invention is to provide a method for producing a coated polyurethane foam, which can efficiently coat a polyurethane foam substrate, and can ensure the soft touch and breathability of the resulting coated polyurethane foam, and its
  • the object of the present invention is to provide a coated polyurethane foam produced by the production method, a garment material formed from the coated polyurethane foam, a bra pad formed from the garment material, and a brassiere cup comprising the bra pad.
  • the method for producing a coated polyurethane foam of the present invention comprises at least one polyisocyanate selected from aliphatic polyisocyanate, alicyclic polyisocyanate and araliphatic polyisocyanate, a high molecular weight polyol, and a low molecular weight active hydrogen group.
  • the step of mechanically foaming the coating layer raw material containing the compound and the foamed coating layer raw material are laminated on the surface of the polyurethane foam base material obtained from the base raw material containing the aromatic polyisocyanate And a step of curing the laminated coating layer raw material to form a polyurethane foam coating layer on the surface of the polyurethane foam base material.
  • the hard foam concentration of the polyurethane foam coating layer is 8 to 45%.
  • the low molecular weight active hydrogen group-containing compound has a first low molecular weight active hydrogen group-containing compound having two active hydrogen groups in one molecule and 3 in one molecule. It is preferable to contain a second low molecular weight active hydrogen group-containing compound having one or more active hydrogen groups.
  • the coating layer material contains 1,3-bis (isocyanatomethyl) cyclohexane and / or 1,4-bis (isocyanatomethyl) cyclohexane as the polyisocyanate. It is suitable to do.
  • the air permeability of the polyurethane foam coating layer is 10 to 120 ml / cm 2 / sec.
  • the method for producing a coated polyurethane foam according to the present invention includes a step of laminating a fabric on the surface of the polyurethane foam coating layer.
  • the coated polyurethane foam of the present invention is characterized by being obtained by the above-described method for producing a coated polyurethane foam.
  • the clothing material of the present invention is characterized by being formed from the above-mentioned coated polyurethane foam.
  • the brassiere pad of the present invention is characterized by being formed from the above-mentioned clothing material.
  • the brassiere cup of the present invention is characterized by comprising the above-mentioned brassiere pad.
  • a mechanically foamed coating layer material is laminated on the surface of a polyurethane foam substrate and cured.
  • the polyurethane foam base material and the polyurethane foam coating layer are laminated.
  • a polyurethane foam coating layer can be formed, and the manufacturing process can be simplified.
  • the polyurethane foam coating layer can be directly laminated on the polyurethane foam base material without using an adhesive, the breathability and soft touch of the resulting coated polyurethane foam can be ensured.
  • the brassiere pad of the present invention and the brassiere cup of the present invention formed using the clothing material formed from the coated polyurethane foam of the present invention it is possible to improve air permeability and tactile sensation.
  • FIG. 1 is a cross-sectional view showing an embodiment of the coated polyurethane foam of the present invention.
  • the coated polyurethane foam 1 includes at least a polyurethane foam substrate 2 and a polyurethane foam coating layer 3 that covers the surface of the polyurethane foam substrate 2 as shown by a solid line in FIG.
  • the polyurethane foam base material 2 is formed of an easily yellowing polyurethane foam that easily turns yellow when exposed to ultraviolet rays or oxidizing gas (nitrogen oxide gas (NOx), etc.), as will be described in detail later.
  • NOx nitrogen oxide gas
  • the thickness of the polyurethane foam substrate 2 is, for example, 1 to 40 mm, preferably 2 to 30 mm.
  • the polyurethane foam coating layer 3 is formed of a yellowing-resistant polyurethane foam that is less susceptible to yellowing than the polyurethane foam substrate 2 as will be described in detail later.
  • the thickness of the polyurethane foam coating layer 3 is, for example, 0.1 to 5 mm, preferably 0.15 to 2 mm, and more preferably 0.15 to 1 mm.
  • coated polyurethane foam 1 may be provided with a fabric 4 that covers the surface of the polyurethane foam coating layer 3 as required, as indicated by phantom lines in FIG.
  • Examples of the fabric 4 include fabrics made of cotton, silk, hemp, mohair, wool, cashmere, polyurethane (spandex), nylon, polyester, rayon, cupra, acetate, and mixed fibers thereof.
  • the fabric 4 is not particularly limited in terms of fiber thickness, weaving method, knitting method, basis weight, function (such as air permeability and antifouling property), and can be appropriately selected.
  • the thickness of the fabric 4 is, for example, 0.01 to 3 mm, preferably 0.05 to 1 mm.
  • the coating layer raw material is mechanically foamed, and the foamed coating layer raw material is laminated on the surface of the polyurethane foam base material 2 and cured to obtain the polyurethane foam coating layer 3. Form.
  • the coating layer raw material contains polyisocyanate, a high molecular weight polyol, and a low molecular weight active hydrogen group-containing compound as essential components.
  • the polyisocyanate is selected from aliphatic polyisocyanate, alicyclic polyisocyanate, and araliphatic polyisocyanate.
  • aliphatic polyisocyanate examples include trimethylene diisocyanate, tetramethylene diisocyanate (TMDI), pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), butylene diisocyanate (for example, 1,2-butylene diisocyanate, 2,3- Aliphatic diisocyanates such as butylene diisocyanate, 1,3-butylene diisocyanate), trimethylhexamethylene diisocyanate (eg 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate), heptamethylene diisocyanate Can be mentioned.
  • TMDI trimethylene diisocyanate
  • PDI pentamethylene diisocyanate
  • HDI hexamethylene diisocyanate
  • butylene diisocyanate for example, 1,2-butylene diisocyanate, 2,3- Aliphatic diisocyanates
  • alicyclic polyisocyanate examples include 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), dicyclohexylmethane diisocyanate (H 12 MDI, for example, 4,4'-dicyclohexylmethane diisocyanate.
  • BIC 2,4'-dicyclohexylmethane diisocyanate, 2,2'-dicyclohexylmethane diisocyanate, and mixtures thereof
  • norbornane diisocyanate NBDI, eg 2,5-bis (isocyanatomethyl) norbornane, 2,6-bis (Isocyanatomethyl) norbornane and mixtures thereof
  • 1,3-cyclopentane diisocyanate 1,3-cyclohexane diisocyanate (eg 1,3-cyclohexane) Xanthane diisocyanate, 1,4-cyclohexane diisocyanate), methylcyclohexane diisocyanate (eg, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), bis (isocyanatomethyl) cyclohexane (BIC, eg, 1, And alicyclic di
  • 1,3-bis (isocyanatomethyl) cyclohexane is obtained by converting cis-1,3-bis (isocyanatomethyl) cyclohexane and trans-1,3-bis (isocyanatomethyl) cyclohexane as geometric isomers.
  • 1,3-bis (isocyanatomethyl) cyclohexane is trans-1,3-bis (isocyanatomethyl) cyclohexane, for example, 20 to 90 mol%, preferably 30 to 80 mol%, more preferably 30 Contains 70 mol%.
  • 1,4-bis (isocyanatomethyl) cyclohexane is prepared in accordance with, for example, the description of International Publication No. 2009/051114, and similar to 1,3-bis (isocyanatomethyl) cyclohexane, As isomers, cis-1,4-bis (isocyanatomethyl) cyclohexane and trans-1,4-bis (isocyanatomethyl) cyclohexane are contained.
  • 1,4-bis (isocyanatomethyl) cyclohexane is trans-1,4-bis (isocyanatomethyl) cyclohexane, for example, 30 to 93 mol%, preferably 40 to 90 mol%, more preferably 50 to 90 mol% is contained.
  • araliphatic polyisocyanate examples include xylylene diisocyanate (XDI, such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and mixtures thereof), tetramethyl xylylene diisocyanate (TMXDI, such as 1,3-tetramethylxylylene diisocyanate, 1,4-tetramethylxylylene diisocyanate, and mixtures thereof), and araliphatic diisocyanates such as ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene.
  • XDI xylylene diisocyanate
  • TMXDI tetramethylxylylene diisocyanate
  • araliphatic diisocyanates such as ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene.
  • polyisocyanates aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates
  • polyisocyanates include those modified products.
  • modified product examples include multimers of the above-mentioned polyisocyanates (for example, dimers such as uretonimine and uretdione, for example, trimers such as the above-described isocyanurates of polyisocyanate and iminooxadiazinedione),
  • examples include oxadiazine trione modified products produced by reaction with carbon dioxide gas.
  • These polyisocyanates can be used alone (only one kind) or in combination of two or more kinds.
  • the aliphatic polyisocyanate preferably includes pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), and modified products thereof
  • the alicyclic polyisocyanate includes 3-isocyanate. Examples include natomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis (isocyanatomethyl) cyclohexane (BIC), and modified products thereof.
  • IPDI isophorone diisocyanate
  • BIC bis (isocyanatomethyl) cyclohexane
  • araliphatic polyisocyanate xylylene diisocyanate (XDI) and its modified body are mentioned.
  • BIC bis (isocyanatomethyl) cyclohexane
  • BIC bis (isocyanatomethyl) cyclohexane
  • BIC bis (isocyanatomethyl) cyclohexane
  • 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane may be used alone, -Bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane may be used in combination.
  • the ratio of 1,4-bis (isocyanatomethyl) cyclohexane to the total amount of 1,3-bis (isocyanatomethyl) cyclohexane and 1,4-bis (isocyanatomethyl) cyclohexane is, for example, 10 to 90 % By mass, preferably 15 to 80% by mass, more preferably 20 to 80% by mass.
  • the breathability and hot compression moldability of the resulting polyurethane foam coating layer 3 can be improved.
  • bis (isocyanatomethyl) cyclohexane (BIC) and other polyisocyanates can be used in combination.
  • bis (isocyanatomethyl) cyclohexane (BIC) with respect to the total amount of polyisocyanate. ) Is, for example, 50% by mass or more, preferably about 70% by mass (specifically, 60 to 80% by mass).
  • the polyisocyanate is prepared by reacting the above-described polyisocyanate, a part or all of the high molecular weight polyol described later, and a part of the low molecular weight active hydrogen compound described below, if necessary, by a known method. It can also be prepared as a polymer. By prepolymerization, the isocyanate monomer concentration in the coating layer material can be reduced. Thereby, the volatilization amount of an isocyanate monomer can be reduced. And the pot life in the reaction process of the polyurethane foam coating layer mentioned later can be lengthened, and workability
  • the high molecular weight polyol is an organic compound having two or more hydroxyl groups and having a number average molecular weight of, for example, 400 or more, preferably 800 or more, more preferably 1,000 or more, and usually 10,000 or less. .
  • high molecular weight polyol examples include polyoxyalkylene polyol, polytetramethylene ether glycol, polyester polyol, polycarbonate polyol, acrylic polyol, polyolefin polyol, and plant-derived polyol.
  • Polyoxyalkylene polyols for example, add (polymerize) alkylene oxide (an alkylene oxide having 2 to 4 carbon atoms) in the presence of a polymerization catalyst using water, ammonia, a low molecular weight alcohol, a low molecular weight amine or the like as an initiator. Can be obtained.
  • low molecular weight alcohol examples include polyhydric alcohols having a molecular weight of less than 400, such as ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-butanediol, and 1,3-butane.
  • the low molecular weight amine is a polyvalent amine having a molecular weight of less than 400, such as methylamine, ethylamine, bis-N, N′-di-tert-butylethylenediamine, JEFLLINK 754 (manufactured by Huntsman), CLEARLINK 1000 ( 3 types of divalent aliphatic amines having two active hydrogens, such as alkanolamines (eg monoethanolamine, diethanolamine, triethanolamine), such as Dorf Ketal Chemicals) and CLEARLINK 3000 (Dorf Ketal Chemicals).
  • alkanolamines eg monoethanolamine, diethanolamine, triethanolamine
  • CLEARLINK 3000 Dorf Ketal Chemicals
  • Trivalent aliphatic amines having active hydrogen active hydrogen derived from amino group and active hydrogen derived from hydroxyl group
  • active hydrogen active hydrogen derived from amino group and active hydrogen derived from hydroxyl group
  • ethylenediamine 1,3-propanediamine, 1,4-buta Diamine, 1,5-pentanediamine, 1,6-hexanediamine, isophoronediamine, norbornenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, dicyclohexylmethanediamine (or A mixture of its isomers), 1,3-xylylenediamine, 1,4-xylylenediamine, and the like, tetravalent aliphatic amines having four active hydrogens, for example, pentavalent having five active hydrogens such as diethylenetriamine
  • examples include aliphatic amines such as aliphatic amines, and aromatic amines such as tolylened
  • water and low molecular weight alcohol are used because the discoloration resistance of the obtained polyurethane foam coating layer 3 can be improved.
  • polymerization catalyst examples include alkali metal catalysts such as potassium hydroxide, sodium hydroxide and cesium hydroxide, and composite metal catalysts such as cyano complexes of zinc and cobalt (for example, described in US Pat. No. 4,477,589). And a phosphazenium compound (for example, a phosphazenium compound catalyst described in Japanese Patent No. 3905638).
  • alkali metal catalysts such as potassium hydroxide, sodium hydroxide and cesium hydroxide
  • composite metal catalysts such as cyano complexes of zinc and cobalt (for example, described in US Pat. No. 4,477,589).
  • a phosphazenium compound for example, a phosphazenium compound catalyst described in Japanese Patent No. 3905638).
  • a phosphazenium compound is preferable. If the polymerization catalyst is a phosphazenium compound, the total unsaturation degree of the polyoxyalkylene polyol can be reduced, and the tensile strength and elongation of the resulting polyurethane foam coating layer 3 can be improved.
  • the hydroxyl value (OHV) of the obtained polyoxyalkylene polyol is, for example, 10 to 300 mgKOH / g, preferably 15 to 150 mgKOH / g, more preferably 18 to 120 mg KOH / g.
  • the total degree of unsaturation which is an indicator of by-product monool, is, for example, 0.07 meq. / G or less, preferably 0.05 meq. / G or less, more preferably 0.03 meq. / G or less, for example, 0.0001 meq. / G or more.
  • hydroxyl value (OHV) and the total unsaturation degree of the polyoxyalkylene polyol are measured by the method described in JIS K1557-3.
  • alkylene oxide examples include ethylene oxide, propylene oxide, and butylene oxide (1,2-butylene oxide, 1,3-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide).
  • alkylene oxides can be used alone (one kind only) or in combination of two or more kinds.
  • propylene oxide is used alone or propylene oxide and ethylene oxide are used in combination.
  • polytetramethylene ether glycol for example, a ring-opening polymer obtained by cationic polymerization of tetrahydrofuran, or an amorphous property obtained by copolymerizing the above-described divalent aliphatic alcohol (for example, neopentyl glycol) with a polymerization unit of tetrahydrofuran.
  • divalent aliphatic alcohol for example, neopentyl glycol
  • examples include polytetramethylene ether glycol.
  • polyester polyol examples include polyester polyols obtained by condensation polymerization of the low molecular weight alcohol and a polybasic acid.
  • a carboxyl having two or more carboxyl groups such as adipic acid, succinic acid, malonic acid, maleic acid, tartaric acid, pimelic acid, sebacic acid, phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid, etc.
  • acids include acids.
  • These polybasic acids can be used alone (only one kind) or in combination of two or more kinds.
  • polyester polyols examples include polycaprolactone polyols obtained by ring-opening polymerization of ⁇ -caprolactone.
  • Polycarbonate polyol is obtained by, for example, ring-opening polymerization of ethylene carbonate using the above-described divalent aliphatic alcohol as an initiator, or copolymerizing the ring-opening polymer obtained thereby and the above-mentioned divalent aliphatic alcohol. Is obtained.
  • polycarbonate polyol examples include amorphous (room temperature liquid) polycarbonate polyol.
  • acrylic polyol examples include a copolymer obtained by copolymerizing a polymerizable monomer having one or more hydroxyl groups and another monomer copolymerizable therewith.
  • Examples of the polymerizable monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2,2-dihydroxymethylbutyl (meth) acrylate, polyhydroxy Examples thereof include alkyl maleates and polyhydroxyalkyl fumarate.
  • the acrylic polyol can be obtained by copolymerizing these monomers in the presence of a suitable solvent and a polymerization initiator.
  • Examples of the plant-derived polyol include low molecular weight polyols such as hydroxyl group-containing natural oils such as castor oil, and modified polyols in which hydroxyl groups are introduced into unsaturated bond-containing natural oils such as palm oil and soybean oil.
  • Examples of the plant-derived polyol include hydroxyl group-containing vegetable oil fatty acids (for example, castor oil fatty acid containing ricinoleic acid, hydrogenated castor oil fatty acid containing 12-hydroxystearic acid) using the above-described low molecular weight polyol as an initiator.
  • vegetable oil-based polyester polyols obtained by condensation reaction of hydroxycarboxylic acids such as those under known conditions.
  • the vegetable oil type polyether addition polyol obtained by adding the above-mentioned alkylene oxide using the above-mentioned plant-derived polyol as an initiator is mentioned.
  • the above-described polyoxyalkylene polyol may be used in combination with the above-described polyester polyol, vinyl polymer-containing polyoxyalkylene polyol, or polyoxyalkylene polyester block copolymer, if necessary.
  • vinyl polymer-containing polyoxyalkylene polyol examples include those obtained by radically polymerizing vinyl monomers such as acrylonitrile and styrene in the presence of radicals in the above-described polyoxyalkylene polyol and stably dispersing them.
  • the ratio of the vinyl polymer in the vinyl polymer-containing polyoxyalkylene polyol is, for example, 15 to 45% by mass.
  • the polyoxyalkylene polyester block copolymer can be obtained, for example, by reacting a polyoxyalkylene polyol with a carboxylic acid anhydride (an anhydride of the polybasic acid described above) and the above-described alkylene oxide.
  • a portion where a hydrogen atom (active hydrogen) of a hydroxyl group of a polyoxyalkylene polyol or a derivative thereof is substituted is represented by the following formula.
  • n is an integer of 1 or more (preferably an integer of 1 to 20).
  • the ratio of the above-described polyester polyol, vinyl polymer-containing polyoxyalkylene polyol or polyoxyalkylene polyester block copolymer in the high-molecular-weight polyol is, for example, 50 parts by mass or less with respect to 100 parts by mass of the polyoxyalkylene polyol. Preferably, it is 30 parts by mass or less.
  • the average functional group number of the high molecular weight polyol is, for example, 1.8 to 6, preferably 2 to 5, and more preferably 2.2 to 4.
  • the average functional group number of the high molecular weight polyol is within the above range, both the elongation and breathability of the resulting polyurethane foam coating layer 3 and the heat resistance can be improved.
  • the melting point of the high molecular weight polyol is, for example, 60 ° C. or less, preferably 50 ° C. or less, more preferably 40 ° C. or less, eg, ⁇ 70 ° C. or more.
  • the melting point of the high molecular weight polyol exceeds 60 ° C., it is necessary to carry out foaming of the coating layer raw material at 60 ° C. or more. During the foaming, the urethanization reaction in the coating layer raw material is promoted and foamed. The viscosity of the coating layer raw material may be significantly increased.
  • the low molecular weight active hydrogen group-containing compound is an organic compound having a number average molecular weight of, for example, less than 400, preferably 18 to 380, more preferably 50 to 350.
  • Examples of the low molecular weight active hydrogen group-containing compound include a first low molecular weight active hydrogen group-containing compound having two active hydrogen groups in one molecule, and a second low molecular weight having three or more active hydrogen groups in one molecule.
  • An active hydrogen group containing compound is mentioned.
  • Examples of the first low molecular weight active hydrogen group-containing compound include divalent aliphatic alcohols among the low molecular weight alcohols described above, divalent aliphatic amines among the low molecular weight amines described above, and alkylene oxides described above. And a low molecular weight polyol to which is added.
  • the second low molecular weight active hydrogen group-containing compound for example, a low molecular weight alcohol other than the above-described divalent aliphatic alcohol, a low molecular weight amine other than the above-described divalent aliphatic amine, and the above-described alkylene oxide are added. And low molecular weight polyols.
  • These low molecular weight active hydrogen group-containing compounds can be used alone (one kind only) or in combination of two or more kinds.
  • These low molecular weight active hydrogen group-containing compounds are preferably used in combination with a first low molecular weight active hydrogen group-containing compound and a second low molecular weight active hydrogen group-containing compound.
  • the ratio of the number of moles of active hydrogen derived from the second low molecular weight active hydrogen group-containing compound to the total number of moles of active hydrogen derived from the low molecular weight active hydrogen group-containing compound is, for example, 1 to 50 mol%, preferably Is from 3 to 40 mol%, more preferably from 7 to 30 mol%.
  • the ratio of the number of moles of active hydrogen derived from the second low molecular weight active hydrogen group-containing compound exceeds the above range, the elongation rate of the resulting polyurethane foam coating layer 3 may decrease. Moreover, the heat resistance of the obtained polyurethane foam coating layer 3 may fall that the ratio of the number-of-moles of active hydrogen originating in a 2nd low molecular weight active hydrogen group containing compound is less than the said range.
  • the low molecular weight active hydrogen compound is blended in an amount of, for example, 2 to 40 parts by mass, preferably 5 to 35 parts by mass with respect to 100 parts by mass of the high molecular weight polyol.
  • a monool monoamine component can be blended with the high molecular weight polyol and / or the low molecular weight active hydrogen compound, if necessary.
  • Examples of the monool / monoamine component include a monool component having one hydroxyl group and a monoamine component having one active hydrogen derived from an amino group.
  • Examples of the monool component include monovalent aliphatic alcohols having 1 to 10 carbon atoms such as methanol, ethanol and isopropyl alcohol, and alkylene oxide adducts of these monovalent aliphatic alcohols, ethylene glycol, propylene glycol, diethylene glycol, Examples thereof include monoalkyl ethers of divalent aliphatic alcohols having 2 to 5 carbon atoms such as 1,4-butanediol.
  • Examples of the monoamine component include monovalent aliphatic amines having one active hydrogen such as dimethylamine and diethylamine.
  • monool / monoamine components can be used alone (only one kind) or in combination of two or more kinds. Further, the content ratio of the monool / monoamine component in the high molecular weight polyol and / or the low molecular weight active hydrogen compound is appropriately set according to the purpose and application.
  • the polyisocyanate, the high molecular weight polyol, and the low molecular weight active hydrogen compound are the isocyanate index (high molecular weight polyol and low molecular weight active hydrogen compound (if necessary, a monool / monoamine component is included) in the coating layer raw material. The same shall apply hereinafter)) such that the ratio of the isocyanate group of the polyisocyanate to the active hydrogen group multiplied by 100 is, for example, 70 to 120, preferably 75 to 115, and more preferably 80 to 110. Blended.
  • the polyisocyanate, the high molecular weight polyol, and the low molecular weight active hydrogen compound have a hard segment concentration of, for example, 8 to 45%, preferably 12 to 40% in the coating layer raw material, More preferably, it is blended so as to be 15 to 35%.
  • the hard segment concentration is lower than 8%, the air flow rate of the obtained polyurethane foam coating layer 3 may be lowered. If the hard segment concentration is higher than 45%, it may be difficult to ensure the coating time.
  • the coating layer material preferably contains a foam stabilizer and a curing catalyst.
  • foam stabilizer examples include L-568, L-580, L-590, L-598, L-600, L-620, L-635, L-638, and L-650 manufactured by Momentive Performance Materials. , L-680, L-682, SC-155, L-5614, L-5617, for example, SZ-1919, SH192, SH190, SZ-580, SRX280A, SZ-584, SF2904, SZ manufactured by Toray Dow Corning -5740M, SZ-1142, SZ-1959, for example, F-607, F-606, F-242TL, F-114, F-348 made by Shin-Etsu Chemical Co., Ltd., for example, DC5598 made by Air Products and Chemicals, DC5933, DC5906, DC5986, DC5950, DC2525, DC2585, DC 070, silicone-based foam stabilizer, such as DC3043, and the like.
  • the foam stabilizer is blended in an amount of, for example, 0.5 to 15 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the high molecular weight polyol.
  • curing catalyst examples include triethylenediamine, bis (N, N-dimethylaminoethyl ether), 1,8-diazabicyclo [5,4,0] undecene-7 (DBU), 1,5-diazabicyclo [4,3,0].
  • Nonene-5 (DBN), amines such as DBU and phenol, octylic acid, oleic acid, p-toluenesulfonic acid, salt with formic acid, amine-based temperature-sensitive catalyst (trade name: TOYOCAT DB30 and DB60, manufactured by Tosoh Corporation) Catalyst, stannous octoate, dibutyltin dilaurate, dioctyltin bis (2-ethylhexyl malate), dimethyltin dineodecanoate, dimethyltin dithioglycolate, dioctyltin dithioglycolate, bismuth octylate, bismuth neodecanoate, zirconium Tetraacetylacetate And metal catalysts such as chromatography and.
  • amines such as DBU and phenol
  • octylic acid such as DBU and phenol
  • oleic acid
  • the activity is preferably suppressed at 50 ° C. or lower, and the original activity is obtained at a high temperature of 70 ° C. or higher in order to improve the covering property of the foamed coating layer raw material to the polyurethane foam base material 2.
  • a so-called temperature-sensitive catalyst can be prepared by mixing the above metal catalyst with a chelating substance.
  • the curing catalyst is blended at a ratio of, for example, 0.001 to 10 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the high molecular weight polyol.
  • the curing catalyst that is solid at room temperature can be dissolved in a solvent in advance and blended with the coating layer raw material.
  • pigments and other additives can be added to the coating layer raw material as optional components.
  • the pigment is blended in order to improve the concealability of the resulting polyurethane foam coating layer 3 with respect to the polyurethane foam substrate 2.
  • pigments with high concealment properties such as titanium oxide.
  • commercially available titanium oxide includes rutile-type titanium oxide having a rutile-type crystal structure and anatase-type titanium oxide having an anatase-type crystal structure.
  • titanium oxides Of these titanium oxides, rutile type titanium oxide is preferable because it has high light resistance as well as high whiteness.
  • rutile type titanium oxide a sulfuric acid method and a chlorine method are mentioned, for example.
  • the production method of rutile titanium oxide is preferably a chlorine method because it has high whiteness.
  • the pigment is blended in the coating layer raw material so that it is contained, for example, in an amount of, for example, 1 to 30% by mass, preferably 2 to 25% by mass, more preferably 3 to 20% by mass, in the resulting polyurethane foam coating layer 3.
  • the concealing effect may be lowered.
  • the content rate of the pigment in the obtained polyurethane foam coating layer 3 exceeds the said range, the polyurethane foam coating layer 3 will become hard and the touch feeling of a coating polyurethane foam may be inferior.
  • a method of kneading and dispersing using three rolls for example, a method of dispersing using a vibration type stirring device, for example, rotating a high shear blade at high speed
  • the pigment is uniformly dispersed in the raw material of the coating layer while pulverizing the secondary agglomerated particles by an appropriate dispersion method such as a method of dispersing the particles.
  • the concealability of the obtained polyurethane foam coating layer 3 to the polyurethane foam base material 2 can be improved.
  • additives include known additives usually used in the production of polyurethane foams, for example, weather resistance improvers such as antioxidants, ultraviolet absorbers, light-resistant stabilizers, anti-discoloration stabilizers, for example, Examples include bleed inhibitors such as acidic substances.
  • antioxidant examples include hindered phenol compounds, organic phosphorus compounds, thioether compounds, hydroxylamine compounds, and the like.
  • hindered phenol compound examples include commercially available products such as Irganox 1135, Irganox 245, Irganox 1135, Irganox 1076, Irganox 1726, Irganox 1520L manufactured by BASF, Adeka Stab AO-80 manufactured by ADEKA, for example, Sumitomo Chemical Co., Ltd. 80 or the like.
  • organic phosphorus compounds are commercially available products such as IRGAFOS 38 and IRGAFOS P-EPQ manufactured by BASF, for example, ADK STAB PEP-4C, ADK STAB PEP-8, ADK STAB 1500, ADK STAB 1500, and ADK STAB 3010 manufactured by ADEKA.
  • JP-302, JP-308, JP-308E, JP-310, JP-312L, JP-333E, JP-318O, JPS-312, JP-13R, JP-318E for example, manufactured by Sumitomo Chemical Co., Ltd.
  • a Sumitizer GP for example, a Sumitizer GP.
  • thioether-based compound examples include IRGANOX PS800FL and IRGANOX PS802FL manufactured by BASF, for example, Adeka Stub AO-412S and Adeka Stub AO-503 manufactured by ADEKA, for example, Yoshitomi DLTP, Yoshitomi DSTP manufactured by API Corporation, Yoshitomi DMTP and the like can be mentioned.
  • Examples of the hydroxylamine compound include IRGASTAB FS 042 manufactured by BASF.
  • ultraviolet absorber examples include benzotriazole compounds and formamidine compounds.
  • benzotriazole compounds examples include Tinuvin 571, Tinuvin 213, Tinuvin 234, and Tinuvin P manufactured by BASF.
  • Examples of the formamidine-based compound include Zikasorb R, Zikasorb BS, ZIKA-FA02, ZIKA-FUA, ZIKA-FUV, ZIKA-UVS3, and ZIKA-UVS4 manufactured by ZIKO.
  • Examples of the light-resistant stabilizer include hindered amine compounds.
  • hindered amine compound examples include Tinuvin 765, Tinuvin 770 and Tinuvin 622LD manufactured by BASF, for example, ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, and ADK STAB LA-72 manufactured by ADEKA. -82, Adekastab LA-87 and the like.
  • the anti-discoloration stabilizer is a stabilizer for suppressing discoloration caused by NOx gas, and examples thereof include semicarbazide (specifically, HN-130, HN-150, HN-300P) manufactured by Nippon Finechem. It is done.
  • the weather resistance improver is blended in an amount of, for example, 0.1 to 5 parts by mass, preferably 0.2 to 2.0 parts by mass, with respect to 100 parts by mass of the high molecular weight polyol.
  • Examples of the acidic substance include oxo acid compounds such as carboxylic acid compounds, phosphoric acid compounds, phosphorous acid compounds, sulfonic acid compounds, and boric acid compounds.
  • carboxylic acid compounds include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, Oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, lactic acid, malic acid, citric acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, melittic acid, cinnamic acid Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, fumaric acid, maleic acid, pyruvic acid, aconitic acid, amino acid, nitrocarboxylic acid.
  • Examples of phosphoric acid compounds and phosphorous acid compounds include diethyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, ethyl acid phosphate, butyl acid phosphate, butyl pyrophosphate, butoxyethyl acid.
  • Examples include phosphate, 2-ethylhexyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate, dibutyl phosphate, bis (2-ethylhexyl) phosphate.
  • the bleed inhibitor is blended at a ratio of, for example, 0.1 to 10 parts by mass, preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the high molecular weight polyol.
  • the polyurethane foam base material 2 is coated with the polyurethane foam base material 2 when the polyurethane foam base material 2 contains a free amine compound such as a tertiary amine catalyst. Migration (bleeding) of the free amine compound can be suppressed.
  • the above-described essential components and, if necessary, the above-mentioned optional components are blended in the above-described blending ratio and stirred.
  • the coating layer material is stirred using a known stirring device while introducing gas.
  • stirring device for example, a batch type stirring device such as a Hobart mixer, for example, an oaks mixer, a curl mixer (manufactured by Chilling Industries Co., Ltd.), a vibration type stirring device (for example, a vibro mixer (cooling)). And a continuous stirring device such as manufactured by Kogyo Co., Ltd.).
  • a Hobart mixer for example, an oaks mixer, a curl mixer (manufactured by Chilling Industries Co., Ltd.), a vibration type stirring device (for example, a vibro mixer (cooling)).
  • a continuous stirring device such as manufactured by Kogyo Co., Ltd.
  • the Hobart mixer mixes the coating layer material and gas by driving a wire-type stirrer in a ball-shaped container under atmospheric pressure.
  • the Oaks mixer continuously introduces the coating layer material and gas between the rotor and the stator, and applies high shearing force to the coating layer material and gas under pressure to mix the coating layer material and gas. To do.
  • the curl mixer has a structure in which a pair of rotating plates provided with a plurality of cylindrical protrusions are arranged so that the protrusions face each other, and one or both of the rotating plates are rotated, The coating layer material and the gas are mixed by continuously introducing the coating layer material and the gas into the gap.
  • a raw material inflow path and a fluid outflow path obtained after mixing are provided in the center and the outer periphery of the rotating plate.
  • a constant pressure is always applied to the raw material being mixed, so that the outflow amount of the raw material can be stabilized.
  • the raw material is introduced from the center direction of the rotating plate, more gas can be introduced, and as a result, the density of the mixture can be reduced.
  • the internal pressure of the mixer can be increased by providing a relief valve in the outflow path. Thereby, it becomes possible to make the bubble size of the mixture finer. Furthermore, by providing a static mixer in front of the inflow path and performing preliminary mixing, even when the raw material is composed of multiple components, it can be mixed efficiently.
  • the vibration type stirring device includes a stirring shaft attached along a longitudinal direction of the flow channel in a cylindrical flow channel sealed by a relief valve, and a stirring blade spirally provided around the stirring shaft.
  • the coating layer material introduced into the flow path and the gas are mixed by vibrating the stirring blade in the axial direction of the stirring shaft.
  • the cylindrical flow path is divided into elements having a predetermined length, and the above-described raw materials can be divided and supplied from any element.
  • the curing catalyst described above when dispersion of the curing catalyst described above is relatively easy, raw materials other than the curing catalyst among the coating layer raw materials are supplied from the element on the upstream side of the flow path, and the curing catalyst is supplied on the downstream side thereof. Can be supplied from the element. Thereby, the production
  • a vibration stirrer can be used in combination in order to disperse the curing catalyst in the mixture obtained using the curl mixer.
  • gas examples include air and inert gases such as nitrogen, carbon dioxide, helium, and argon.
  • a physical foaming agent such as liquefied chlorofluorocarbon gas or a chemical foaming agent such as water or an azo compound can be used in combination with the above-described gas, if necessary.
  • the viscosity of the foamed coating layer raw material at 30 ° C. is, for example, 50 to 30,000 mPa ⁇ s, preferably 100 to 10,000 mPa ⁇ s, more preferably Is 150 to 5,000 mPa ⁇ s.
  • the foamed coating layer raw material has a viscosity at 30 ° C. higher than 30,000 mPa ⁇ s, the foaming property may be impaired, and the density of the foamed coating layer raw material may be significantly increased. Further, when the viscosity of the foamed coating layer raw material at 30 ° C. is lower than 50 mPa ⁇ s, the performance of retaining bubbles introduced by stirring is impaired, and the density of the foamed coating layer raw material is remarkably increased. There is a case.
  • the foamed coating layer raw material is laminated on the surface of the polyurethane foam substrate 2.
  • the polyurethane foam base material 2 is obtained by reacting a base material containing an aromatic polyisocyanate.
  • the base material contains a polyisocyanate containing an aromatic polyisocyanate and the above-described high molecular weight polyol.
  • the above-mentioned low molecular weight active hydrogen compound, the above-mentioned additive, a well-known foaming agent, etc. can be suitably mix
  • aromatic polyisocyanate examples include tolylene diisocyanate (2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or a mixture thereof) (TDI), phenylene diisocyanate (m-phenylene diisocyanate, p-phenylene diisocyanate, Or a mixture thereof), 4,4′-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, 2, 2'-diphenylmethane diisocyanate or a mixture thereof (MDI), 4,4'-toluidine diisocyanate (TODI), 4,4'-diphenyl ether diisocyanate Isocyanate, and the like.
  • TDI tolylene diisocyanate (2,4-toly
  • polyisocyanate in addition, in addition to aromatic polyisocyanate, the above-mentioned polyisocyanate can also be mix
  • a premix prepared by blending the above-described high molecular weight polyol with the above-described low molecular weight active hydrogen compound, the above-described additive, a known foaming agent, and the like,
  • the polyisocyanate is reacted with an appropriate method (for example, slab method).
  • the air flow rate of the polyurethane foam base material 2 is, for example, 1 to 400 ml / cm 2 / sec, preferably 10 to 350 ml / cm 2 / sec, more preferably. Is 30 to 300 ml / cm 2 / sec.
  • the core density of the polyurethane foam substrate 2 is, for example, 10 to 100 kg / cm 3 , preferably 15 to 70 kg / cm 3 , more preferably 18 to 60 kg / cm 3. It is.
  • the number of cells (bubbles) per unit area (1 cm 2 ) of the polyurethane foam substrate 2 is, for example, 25 to 900 / cm 2 , preferably 50 to 800 / cm 2 , more preferably 80 to 600. Pieces / cm 2 .
  • the number of cells per unit area of the polyurethane foam substrate 2 is less than 25 / cm 2 , voids and irregularities are likely to occur in the coating layer. Further, if the number of cells per unit area of the polyurethane foam base material 2 exceeds 900 / cm 2 , sufficient air permeability may not be obtained.
  • the number of cells per unit area of the polyurethane foam substrate 2 can be measured, for example, by the following method.
  • a thin black ink is applied to the smooth cut surface of the polyurethane foam substrate 2.
  • the coated surface is magnified 20 times using a CCD camera (manufactured by Keyence Corporation, microscope VHX-900) and displayed on the display.
  • An area corresponding to 1 cm 2 of the polyurethane foam substrate 2 is output on the same display, and the number of cells contained in the area is counted visually to obtain the number of cells per unit area (1 cm 2 ).
  • the foamed coating layer material is laminated on the surface of the polyurethane foam base material 2 without any particular limitation.
  • the foamed coating layer material is once discharged onto a release sheet, After coating with a blade or the like to a desired thickness, the film is laminated on the surface of the polyurethane foam substrate 2. According to this method, the surface of the obtained polyurethane foam coating layer 3 becomes smooth, and the design properties can be improved.
  • the release sheet can be applied with foamed coating layer raw material, and does not significantly deform, melt, deteriorate, decompose, or burn during the curing process of the foamed coating layer raw material, and has stable release performance. If it has, it will not specifically limit about the structure and material.
  • Examples of the material of the release sheet include polyethylene, polypropylene, polymethylpentene, which is a cyclic polyolefin copolymer, silicone, fluororesin, and polyester resin coated with silicone.
  • a release sheet for example, in addition to the resin film (single layer) made of the above-described material, a paper, a film and a fibrous sheet coated with a release agent, similarly, paper, film and fiber And a laminate of a resin having a releasing property on a sheet-like sheet.
  • the thickness of the coating layer material discharged onto the release sheet is, for example, 0.1 to 5 mm, preferably 0.15 to 2 mm, and more preferably 0.2 to 1 mm.
  • the thickness of the coating layer material discharged onto the release sheet is less than 0.1 mm, a part of the discharged coating layer material is absorbed by the polyurethane foam base material 2 over time, and the polyurethane foam The component of the base material 2 moves to the surface of the polyurethane foam coating layer 3, and the concealing effect of the polyurethane foam base material 2 by the polyurethane foam coating layer 3 may be lowered.
  • the thickness of the coating layer raw material discharged on the release sheet is larger than 5 mm, the air permeability of the obtained polyurethane foam coating layer 3 tends to be lowered.
  • the coating layer material discharged onto the release sheet is laminated on the polyurethane foam base material 2
  • the coating layer material discharged onto the release sheet is appropriately thickened so that the coating layer material becomes polyurethane foam. Absorption by the base material 2 can also be suppressed.
  • the coating layer material is prepolymerized with polyisocyanate and a high molecular weight polyol, and if necessary, a low molecular weight active hydrogen compound, and then foamed, for example, a coating layer material .
  • a method for adding a thixotropic agent such as aerosil in advance, and then foaming, for example, the coating layer material discharged on the release sheet is preliminarily heated before being brought into contact with the polyurethane foam substrate 2 A method is mentioned.
  • the heating temperature at this time is, for example, 50 to 120 ° C., preferably 60 to 110 ° C., more preferably 70 to 100 ° C.
  • the heating temperature is lower than 50 ° C., the time until the desired viscosity is reached becomes longer and the productivity may be lowered.
  • the heating temperature is higher than 120 ° C., the coating layer raw material may be excessively cured.
  • the heating time at this time is, for example, 10 seconds to 20 minutes, preferably 20 seconds to 15 minutes, and preferably 30 seconds to 10 minutes.
  • the heating time is less than 10 seconds, the fluctuation of the heating temperature greatly affects the viscosity of the coating layer raw material, which may reduce the production stability. If the heating time exceeds 20 minutes, the productivity may decrease.
  • the coating layer raw material thickened by heating is laminated on the surface of the polyurethane foam substrate 2 to produce a release sheet / coating layer raw material / polyurethane foam substrate laminate.
  • the method for laminating the coating layer raw material on the surface of the polyurethane foam base material 2 is not particularly limited, and the coating layer raw material can be laminated on the polyurethane foam base material 2.
  • the base material 2 can also be laminated.
  • the polyurethane foam coating layer 3 When the surface of the polyurethane foam coating layer 3 is coated with the fabric 4, the polyurethane foam coating layer 3 is laminated on the surface of the polyurethane foam base material 2, and then heated to form a coating layer raw material. Allow the reaction to proceed.
  • the heating temperature and the heating time at this time are appropriately set so that the coating material is reacted to such an extent that the release sheet can be easily peeled off.
  • the heating temperature at this time is, for example, 50 to 150 ° C., preferably 60 to 140 ° C., and more preferably 70 to 120 ° C.
  • the heating time at this time is, for example, 10 seconds to 20 minutes, preferably 20 seconds to 15 minutes, and more preferably 30 seconds to 10 minutes.
  • the heating time is less than 10 seconds, the fluctuation of the heating temperature greatly affects the viscosity of the coating layer raw material, which may reduce the production stability. If the heating time exceeds 20 minutes, the productivity may decrease.
  • the release sheet is peeled off, and the fabric 4 is laminated on the surface of the polyurethane foam coating layer 3.
  • the adhesion strength of the fabric 4 to the polyurethane foam coating layer 3 is, for example, 0.3 to 10 N, preferably 0.5 to 7 N, and more preferably 0.7 to 5 N. It is.
  • the fabric 4 may peel off during use of the coated polyurethane foam 1 laminated with the fabric 4. Moreover, when the adhesive strength of the fabric 4 exceeds 10 N, the touch feeling of the coated polyurethane foam 1 on which the fabric 4 is laminated may become hard.
  • the coating layer material foamed on the surface of the polyurethane foam base material 2 is directly discharged, and then a doctor blade A method of forming a coating layer while adjusting the coating thickness by, for example, extruding a coating layer raw material foamed by a T die or the like while thinning it to a predetermined thickness and laminating it on the polyurethane foam substrate 2 A method is also mentioned.
  • the laminated coating layer raw material is cured to form the polyurethane foam coating layer 3 on the surface of the polyurethane foam substrate 2.
  • the temperature for curing the coating layer raw material is, for example, 80 to 200 ° C., preferably 90 to 180 ° C., more preferably 100 to 160 ° C.
  • the temperature for curing the coating layer material is lower than 80 ° C., the time until the coating layer material is cured may be long. If the temperature for curing the coating layer raw material is higher than 200 ° C., the coated polyurethane foam 1 may be deteriorated by heat, and the mechanical strength may be lowered or discoloration may occur.
  • the time for curing the coating layer raw material is, for example, 10 seconds to 12 minutes, preferably 20 seconds to 7 minutes, and more preferably 30 seconds to 5 minutes.
  • the time for curing the coating layer raw material is less than 10 seconds, the fluctuation of the heating temperature greatly affects the viscosity of the coating layer raw material, which may reduce the production stability. If the time for curing the coating layer raw material exceeds 12 minutes, the productivity may decrease.
  • the coated polyurethane foam 1 in which the polyurethane foam coating layer 3 is formed on the surface of the polyurethane foam substrate 2 is produced.
  • the air permeability of the coated polyurethane foam 1 obtained is, for example, 10 to 120 ml / cm 2 / sec, preferably 20 to 110 ml / cm 2 / sec, More preferably, it is 30 to 100 ml / cm 2 / sec.
  • the air flow rate of the coated polyurethane foam 1 is lower than 10 ml / cm 2 / sec, it may be steamed and a refreshing feeling may not be obtained when it is used for clothing.
  • the air flow rate of the coated polyurethane foam 1 is higher than 120 ml / cm 2 / sec, the touch feeling of the coated polyurethane foam 1 may be inferior.
  • the tactile sensation of the obtained coated polyurethane foam 1 can be evaluated based on, for example, a change in hardness of the obtained coated polyurethane foam 1 on the basis of the hardness of the polyurethane foam substrate 2.
  • the hardness of the coated polyurethane foam 1 and the polyurethane foam substrate 2 is measured using, for example, an F-type hardness meter.
  • the amount of change in the F-type hardness of the coated polyurethane foam 1 with respect to the hardness of the polyurethane foam substrate 2 is, for example, 0 to 30, preferably 0 to 20, and more preferably 0 to 10.
  • the touch feeling of the coated polyurethane foam 1 may be inferior.
  • the apparent density of the polyurethane foam coating layer alone (showing the polyurethane foam coating layer 3 produced as described above without being laminated on the polyurethane foam base material 2.
  • the same applies hereinafter) is, for example, 0.05 to 0.6 g. / Cc, preferably 0.07 to 0.5 g / cc, more preferably 0.1 to 0.4 g / cc.
  • the heat resistance of the polyurethane foam coating layer 3 may be reduced. Further, if the apparent density of the coating layer alone is larger than 0.6 g / cc, the air permeability of the polyurethane foam coating layer 3 may be lowered.
  • the change amount ( ⁇ b) of the b value before and after the ultraviolet irradiation by the QUV weathering tester of the coating layer alone is, for example, 6 or less, preferably 4 or less, more preferably 2 or less.
  • ⁇ b of the coating layer alone exceeds 6, there may be a case where the effect of suppressing discoloration of the polyurethane foam base material 2 due to coating cannot be obtained sufficiently.
  • the storage elastic modulus at 25 ° C. in the dynamic viscoelasticity measurement (measured by the method described in Examples described later) of the coating layer alone is, for example, 0.3 to 5 MPa, preferably 0.45 to 4 MPa, More preferably, it is 0.6 to 3.5 MPa.
  • the storage elastic modulus at 25 ° C. of the coating layer alone exceeds 5 MPa, the polyurethane foam coating layer 3 becomes too hard and the touch may be lowered. There exists a possibility that the intensity
  • the obtained coated polyurethane foam 1 can be molded into a desired shape by compression molding under heating such as a hot press.
  • This heat compression moldability can be evaluated by the temperature at which the storage elastic modulus in the above dynamic viscoelasticity measurement becomes equal to 0.3 MPa corresponding to the rubber-like fluidization region. It has been experimentally investigated that the heat compression moldability can be evaluated by a temperature at which the storage elastic modulus in the dynamic viscoelasticity measurement becomes equal to 0.3 MPa corresponding to the rubber-like fluidized region.
  • the temperature at which the storage elastic modulus of the coating layer alone becomes equal to 0.3 MPa is, for example, 140 to 230 ° C., preferably 150 to 220 ° C., more preferably 160 to 210 ° C.
  • the hot compression molding of the coated polyurethane foam 1 is usually performed at 180 to 200 ° C.
  • the temperature at which the storage elastic modulus of the coating layer alone becomes equal to 0.3 MPa is 140 ° C. or less
  • the polyurethane foam coating layer 3 may be melted or decomposed when hot compression molding is performed at 180 ° C. or more.
  • the temperature at which the storage elastic modulus of the single coating layer becomes equal to 0.3 MPa is 230 ° C. or more, it may be difficult to mold at a heat compression temperature of about 200 ° C.
  • a mechanically foamed coating layer material is laminated on the surface of a polyurethane foam substrate and cured.
  • the polyurethane foam base material and the polyurethane foam coating layer are laminated.
  • a polyurethane foam coating layer can be formed, and the manufacturing process can be simplified.
  • the polyurethane foam coating layer can be directly laminated on the polyurethane foam base material without using an adhesive, the breathability and soft touch of the resulting coated polyurethane foam can be ensured.
  • Examples of the use of the obtained coated polyurethane foam 1 include body pressure dispersion materials, shape retaining materials, sound absorbing materials, and shock absorbing materials in the fields of automobiles, furniture, bedding, electronic materials, medical care, clothing, hygiene materials, and the like. It can be effectively used as an elastic material such as a vibration absorbing material and an optical material.
  • the coated polyurethane foam 1 includes, for example, a seat, a headrest, a pillow, a mattress, and the like, a sofa, a cushioning material for nursing care, a leisure sheet, a supporter, a shape retention material for wigs, a filter, a cover for a microphone, and an earphone.
  • the coated polyurethane foam 1 is preferably used as a body pressure buffer material for clothing or shoes because it has a soft touch, excellent discoloration resistance, excellent breathability and excellent heat compression moldability.
  • the brassiere pad of the present invention and the brassiere cup of the present invention which are formed using a clothing material formed from the coated polyurethane foam of the present invention, it is possible to improve air permeability and tactile sensation.
  • the purity of the obtained 1,4-bis (isocyanatomethyl) cyclohexane as measured by gas chromatography was 99.9%, and the trans / cis ratio as determined by 13 C-NMR was 86/14 on a molar basis.
  • Polyisocyanate B 1,3-bis (isocyanatomethyl) cyclohexane (Mitsui Chemicals, trade name: Takenate 600)
  • the purity by gas chromatography measurement was 99.9%, and the trans / cis ratio by 13 C-NMR measurement was 26/74.
  • Polyisocyanate D Isophorone diisocyanate (Evonik Degussa Japan, trade name: VESTANAT IPDI) (2) High molecular weight polyol (High molecular weight polyol A) Polyoxyalkylene triol obtained by addition polymerization of propylene oxide and then ethylene oxide using glycerin as an initiator and potassium hydroxide as a catalyst according to a conventional method (hydroxyl value: 33.0 mg KOH / g, oxyethylene unit content: 14%, total Unsaturation degree: 0.065 meq./g).
  • High molecular weight polyol C Polyoxypropylene glycol obtained by addition polymerization of propylene oxide using propylene glycol as an initiator and potassium hydroxide as a catalyst according to a conventional method (hydroxyl value: 56.1 mgKOH / g, total unsaturation: 0.035 meq./g).
  • Low molecular weight active hydrogen compound A 1,4-butanediol (1,4-BD, manufactured by Mitsubishi Chemical Corporation) and trimethylolpropane (TMP, manufactured by Mitsubishi Gas Chemical Company) were weighed in a container at a ratio of 70/30 (mass ratio), and 80 ° C.
  • a mixed solution of 1,4-butanediol and trimethylolpropane obtained by heating and dissolving for 2 hours and then dehydrating under reduced pressure.
  • the preliminary dispersion was prepared by blending 50 parts by mass of pigment and 50 parts by mass of high molecular weight polyol C and kneading them with a three roll.
  • Polyurethane foam base material As the polyurethane foam base material, a slab foam prepared from a base material containing tolylene diisocyanate (TDI) was used.
  • the core density (measured according to JIS K7222 (2005)) of the obtained polyurethane foam substrate was 52 kg / cm 3 .
  • the air permeability (measured according to JIS K6400-7 (2004) B method) of the obtained polyurethane foam substrate was 70 ml / cm 2 / sec.
  • the number of cells per unit area (measured by the evaluation method described above) of the obtained polyurethane foam substrate was 585 cells / cm 2 .
  • the difference ⁇ b between the b value before the light resistance evaluation and the b value after the light resistance evaluation of the obtained polyurethane foam substrate was 16.3 (b value after the light resistance evaluation (14.6) ⁇ light resistance). The b value before evaluation (-1.7)).
  • light resistance evaluation of the obtained polyurethane foam base material was measured with the evaluation method mentioned later.
  • Example 1 Coated polyurethane foam
  • the above-mentioned raw materials (other than the curing catalyst and foam stabilizer) were weighed in the number of parts shown in Table 1 and mixed in a laboratory at 23 ° C. and 55% relative humidity until they were uniform.
  • Table 1 shows the hard segment concentration of the obtained mixture.
  • the coating layer raw material is stirred for 5 minutes at a revolution speed of 180 rpm in a nitrogen atmosphere.
  • the coating layer raw material was foamed.
  • the density of the coating layer raw material 10 minutes after the start of stirring was measured. The results are shown in Table 3.
  • the foamed coating layer material was applied onto a release sheet using a baker type film applicator (manufactured by Yasuda Seiki Seisakusho) with a gap width adjusted to 0.8 mm, and then adjusted to 80 ° C. It was preheated for 3.5 minutes in a warm oven to increase the viscosity.
  • a baker type film applicator manufactured by Yasuda Seiki Seisakusho
  • a polyurethane foam base material cut to a thickness of 10 mm is laminated on the thickened coating layer raw material, heated for another 2 minutes, and then released from the oven from the release sheet / coating layer raw material / polyurethane.
  • the foam substrate laminate was removed.
  • the laminate of release sheet / coating layer material / polyurethane foam substrate was heated in an oven adjusted to 135 ° C. for 3 minutes to cure the coating layer material to form a polyurethane foam coating layer.
  • coated polyurethane foam was allowed to stand in a laboratory at 23 ° C. and a relative humidity of 55% for 2 days, then cut into a predetermined shape and subjected to the physical property evaluation shown in Table 3.
  • Coated polyurethane foam with fabric After removing the release sheet / coating layer raw material / polyurethane foam substrate laminate from the oven, the release sheet was immediately peeled off, and the fabric was brought into close contact with the coating layer raw material so that no gap was formed. .
  • the laminate of the fabric / coating layer material / polyurethane foam substrate was heated in an oven adjusted to 135 ° C. for 3 minutes to cure the coating layer material to form a polyurethane foam coating layer.
  • coated polyurethane foam was allowed to stand in a laboratory at 23 ° C. and a relative humidity of 55% for 2 days, then cut into a predetermined shape and subjected to the physical property evaluation shown in Table 3. (Coating layer alone) Separately, in the same manner as the preparation of the coating material, a sample (bubbled coating material) used for evaluating the physical properties of the coating layer alone was prepared.
  • the obtained sample was applied on a release sheet using a Baker type film applicator (manufactured by Yasuda Seiki Seisakusho) with a gap width adjusted to 0.5 mm, and then in an oven adjusted to 80 ° C.
  • the sample was preheated for 3 minutes and then heated in an oven adjusted to 135 ° C. for 3 minutes to cure the sample to obtain a single coating layer as a sheet-like foam.
  • Example 2 A coated polyurethane foam having a coated polyurethane foam, a coating layer alone, and a fabric (Example 2 and Example 7) in the same manner as in Example 1 except that the raw materials shown in Table 1 were blended in the blending amounts shown in Table 1. ) was prepared.
  • Example 11 Polyisocyanate A, high molecular weight polyol A and high molecular weight polyol C are weighed according to the number of parts in Table 2 in a reaction vessel equipped with a nitrogen introduction tube, a thermometer, a cooling tube, and a stirrer at 80 to 85 ° C. with good stirring. The reaction was performed for about 2 hours. Next, it was confirmed that the isocyanate group content had dropped to 7.1% by mass, and an isocyanate group-terminated prepolymer was obtained.
  • Table 2 shows the hard segment concentration of the obtained isocyanate group-terminated prepolymer.
  • the obtained isocyanate group-terminated prepolymer was defoamed under reduced pressure, and then the viscosity at 30 ° C. was measured by the measurement method described later. The results are shown in Table 4.
  • the coating layer material and nitrogen as the foaming gas were supplied toward the center of the rotating plate from the inlet provided in the outer peripheral portion of the rotating plate housed inside the mixer housing.
  • the obtained isocyanate group-terminated prepolymer and resin premix were supplied to a curl mixer at a mass ratio of 100: 42.4.
  • nitrogen gas was supplied from another inlet.
  • the flow rate of nitrogen gas was twice that of the coating layer material (when supplying the coating layer material at 500 cc / min, the flow rate of nitrogen gas was 1000 cc / min).
  • the upper rotating body and the lower rotating body of the curl mixer were rotated in the opposite directions at 600 rpm to foam the coating layer material.
  • the residence time of the coating layer raw material inside the mixer was about 30 seconds when the raw material supply rate was 500 cc / min.
  • the density of the coating layer raw material 10 minutes after the start of stirring was measured. The results are shown in Table 4.
  • Example 1 a coated polyurethane foam, a coated polyurethane foam having a fabric, and a coating layer alone were obtained in the same manner as in Example 1.
  • Example 12 Except for blending the raw materials shown in Table 2 in the blending amounts shown in Table 2, in the same manner as in Example 11, after preparing an isocyanate group-terminated prepolymer (isocyanate group content of 12.17%) and a resin premix, Both were supplied to the curl mixer at a mass ratio of 100: 49.4 to foam the coating layer raw material.
  • Example 1 Using the obtained coating layer raw material, a coated polyurethane foam, a coated polyurethane foam having a fabric, and a coating layer alone were obtained in the same manner as in Example 1.
  • Example 13 Except for blending the raw materials shown in Table 2 in the blending amounts shown in Table 2, in the same manner as in Example 11, after preparing an isocyanate group-terminated prepolymer (isocyanate group content of 17.19%) and a resin premix, Both were supplied to the curl mixer at a mass ratio of 100: 56.8 to foam the coating layer material.
  • Example 1 Using the obtained coating layer raw material, a coated polyurethane foam, a coated polyurethane foam having a fabric, and a coating layer alone were obtained in the same manner as in Example 1.
  • a value obtained by dividing the measured mass (unit: g) by the volume (10 cc) of the foamed coating layer raw material was defined as the density of the foamed coating layer raw material.
  • (3) Apparent density (unit: g / cc) and thickness (unit: mm) of the coating layer alone The obtained coating layer alone was punched into a size of 3 cm ⁇ 7 cm, and then the apparent density was measured based on the method described in JIS K7222 (2005). The thickness was measured. The results are shown in Tables 3 and 4.
  • (4) Tensile strength (TS, unit: kPa) and elongation at break (EL, unit:%) of the coating layer alone The tensile test of the coating layer alone was performed based on the method described in JIS K-6400-5 (2004).
  • test piece was punched with a No. 2 dumbbell, and the tensile strength and elongation at break were measured at a pulling speed of 500 mm / min using a tensile testing machine (trade name: RTG-1310, manufactured by A & D). It was measured. The results are shown in Tables 3 and 4.
  • Tactile sensation (storage modulus, unit: MPa / 25 ° C.) and thermal compression moldability (unit: ° C.) of the coating layer by dynamic viscoelasticity measurement of the coating layer alone Using a dynamic viscoelasticity measuring device (trade name: DVA-200, manufactured by IT Measurement Control Co., Ltd.), the storage elastic modulus of a single coating layer cut to a width of 5 mm was measured at a rate of 3 ° C./min in an air atmosphere. The measurement was performed at a frequency of 10 Hz while the temperature was raised from ⁇ 100 ° C. to 250 ° C.
  • Tables 3 and 4 show the storage elastic modulus at 25 ° C. and the temperature at which the storage elastic modulus becomes 0.3 MPa.
  • the air flow rate of the coating layer alone, the coated polyurethane foam, and the coated polyurethane foam having the fabric is JIS K6400-7 (2004) B. It was measured based on the method described in the method. The results are shown in Tables 3 and 4.
  • an ultraviolet irradiation test apparatus manufactured by Sanyo Trading Co., Ltd., trade name: QUV weathering tester
  • a black panel temperature of 50 ° C. and ultraviolet rays with a short wavelength (wavelength of 270 to 400 nm) are emitted with an irradiance of 28 W / Irradiation was performed for 24 hours under the condition of m 2 .
  • the coated polyurethane foam obtained by the method for producing a coated polyurethane foam of the present invention is, for example, a body pressure dispersing material, a shape-retaining material in the fields of automobiles, furniture, bedding, electronic materials, medical care, clothing, hygiene materials, It can be used as an elastic material such as a sound absorbing material, a shock absorbing material, a vibration absorbing material, and an optical material.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
PCT/JP2013/057663 2012-03-19 2013-03-18 被覆ポリウレタンフォームの製造方法、被覆ポリウレタンフォーム、衣料材料、ブラジャーのパッド、および、ブラジャーのカップ Ceased WO2013141207A1 (ja)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017006556A1 (ja) * 2015-07-08 2017-01-12 セーレン株式会社 エンボス加工用複合材およびエンボス加工品
JPWO2017038910A1 (ja) * 2015-09-01 2018-08-09 三井化学株式会社 緩衝材、塗装用自動運動装置用緩衝材、緩衝材付自動運動装置および緩衝材付塗装用自動運動装置
CN109890863A (zh) * 2016-11-16 2019-06-14 三井化学株式会社 聚氨酯泡沫体、衣料用材料、胸罩衬垫、胸罩罩杯、及聚氨酯泡沫体的制造方法
JP2019178519A (ja) * 2018-03-30 2019-10-17 アキレス株式会社 床材
US20220024177A1 (en) * 2018-11-21 2022-01-27 Silueta (Private) Limited Moulded composite article formed from laminates
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JPWO2023228876A1 (zh) * 2022-05-27 2023-11-30
TWI836978B (zh) * 2022-09-08 2024-03-21 美商帕拉萊斯集團國際有限責任公司 墊體
JP7815427B2 (ja) 2022-05-27 2026-02-17 三井化学株式会社 熱可塑性ポリウレタン樹脂、フィルムおよび塗装保護フィルム

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CN110114383B (zh) * 2017-03-31 2021-09-17 三井化学株式会社 软质聚氨酯泡沫体、衣料用材料、胸罩衬垫、胸罩罩杯、及软质聚氨酯泡沫体的制造方法
KR102003207B1 (ko) * 2017-09-25 2019-07-25 진양산업 주식회사 구연산을 이용한 변색 지연 소재 및 그 제조 방법

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242211A (ja) * 1988-03-24 1989-09-27 Inoue Mtp Co Ltd 多層異硬度クッション体の製造方法およびその製造用型
JPH0530115U (ja) * 1991-09-25 1993-04-20 アキレス株式会社 衣料用パツド
JPH08337903A (ja) * 1995-06-08 1996-12-24 Datsuchiesu:Kk ブラジャー等のパッド
JP2002052551A (ja) * 2000-06-28 2002-02-19 World Properties Inc 複合ポリウレタンフォームとその製造方法
JP2005059358A (ja) * 2003-08-11 2005-03-10 Inoac Corp 積層発泡体及びその製造方法
JP2011137275A (ja) * 2010-01-04 2011-07-14 Toyo Quality One Corp ポリウレタンフォーム製ブラジャーパッド及びその製造方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009051114A1 (ja) * 2007-10-15 2009-04-23 Mitsui Chemicals Polyurethanes, Inc. ポリウレタン樹脂
JP5386144B2 (ja) * 2007-11-27 2014-01-15 三井化学株式会社 ポリウレタンフォームおよびポリウレタンフォーム用ポリイソシアネート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01242211A (ja) * 1988-03-24 1989-09-27 Inoue Mtp Co Ltd 多層異硬度クッション体の製造方法およびその製造用型
JPH0530115U (ja) * 1991-09-25 1993-04-20 アキレス株式会社 衣料用パツド
JPH08337903A (ja) * 1995-06-08 1996-12-24 Datsuchiesu:Kk ブラジャー等のパッド
JP2002052551A (ja) * 2000-06-28 2002-02-19 World Properties Inc 複合ポリウレタンフォームとその製造方法
JP2005059358A (ja) * 2003-08-11 2005-03-10 Inoac Corp 積層発泡体及びその製造方法
JP2011137275A (ja) * 2010-01-04 2011-07-14 Toyo Quality One Corp ポリウレタンフォーム製ブラジャーパッド及びその製造方法

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2017006556A1 (ja) * 2015-07-08 2018-04-19 セーレン株式会社 エンボス加工用複合材およびエンボス加工品
WO2017006556A1 (ja) * 2015-07-08 2017-01-12 セーレン株式会社 エンボス加工用複合材およびエンボス加工品
JPWO2017038910A1 (ja) * 2015-09-01 2018-08-09 三井化学株式会社 緩衝材、塗装用自動運動装置用緩衝材、緩衝材付自動運動装置および緩衝材付塗装用自動運動装置
US10913251B2 (en) 2015-09-01 2021-02-09 Mitsui Chemicals, Inc. Buffer material, buffer material for coating robot, robot with buffer material, and coating robot with buffer material
CN109890863A (zh) * 2016-11-16 2019-06-14 三井化学株式会社 聚氨酯泡沫体、衣料用材料、胸罩衬垫、胸罩罩杯、及聚氨酯泡沫体的制造方法
JP7051539B2 (ja) 2018-03-30 2022-04-11 アキレス株式会社 床材
JP2019178519A (ja) * 2018-03-30 2019-10-17 アキレス株式会社 床材
US20220024177A1 (en) * 2018-11-21 2022-01-27 Silueta (Private) Limited Moulded composite article formed from laminates
US11780208B2 (en) * 2018-11-21 2023-10-10 Silueta (Private) Limited Moulded composite article formed from laminates
JPWO2023228876A1 (zh) * 2022-05-27 2023-11-30
WO2023228876A1 (ja) * 2022-05-27 2023-11-30 三井化学株式会社 熱可塑性ポリウレタン樹脂、フィルムおよび塗装保護フィルム
JP7815427B2 (ja) 2022-05-27 2026-02-17 三井化学株式会社 熱可塑性ポリウレタン樹脂、フィルムおよび塗装保護フィルム
TWI819782B (zh) * 2022-09-08 2023-10-21 美商帕拉萊斯集團國際有限責任公司 墊體
TWI836978B (zh) * 2022-09-08 2024-03-21 美商帕拉萊斯集團國際有限責任公司 墊體

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