Classifications

• • 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
• • 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
• • 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
  • C08G18/30—Low-molecular-weight compounds
• • 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
• • 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
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2209/00—Properties of the materials
  • D06N2209/16—Properties of the materials having other properties
  • D06N2209/1692—Weather resistance

Definitions

• the present invention relates to synthetic leather.
• the moisture-curable polyurethane hot melt resin composition is widely used in the production of synthetic leather because of its excellent mechanical strength and flexibility.
• split leather including a floor leather, an adhesive layer, and a skin layer is similar in appearance and texture to natural leather, and therefore, the demand for natural leather is increasing with the recent price increase of natural leather.
• a resin composition forming the split leather for example, a resin composition containing dimethylformamide, a urethane resin, and a long-chain fatty acid salt of a non-alkali metal is disclosed (for example, see Patent Document 1). ..).
• dimethylformamide will be difficult to use in the future due to concern about health hazards, due to SVHC regulations in Europe, voluntary regulations by major apparel manufacturers, and VOC emission regulations in China. To be done.
• the problem to be solved by the present invention is to provide synthetic leather having excellent solidification rate, weather resistance, and uniform appearance.
• the present invention has a cured product layer of a moisture-curable polyurethane hot melt resin composition which is a reaction product of a polyol (A) and a polyisocyanate (B) and contains a urethane prepolymer (i) having an isocyanate group.
• Synthetic leather wherein the polyol (A) contains a crystalline polyester polyol (a1) made of hexanediol as a raw material and does not contain an aromatic polyester polyol (a'1). It provides synthetic leather.
• the synthetic leather of the present invention is excellent in solidification speed, weather resistance, and uniformity of appearance, and can be particularly suitably used as split leather.
• the moisture-curable polyurethane hot melt resin composition used in the present invention is a reaction product of a specific polyol (A) and a polyisocyanate (B), and contains a urethane prepolymer (i) having an isocyanate group. is there.
• the polyol (A) contains a crystalline polyester polyol (a1) made of hexanediol as a raw material, and does not contain an aromatic polyester polyol (a'1).
• the aromatic polyester polyol (a'1) When the aromatic polyester polyol (a'1) is used as a raw material, the weather resistance becomes poor.
• the aromatic polyester polyol (a'1) is constituted if at least one aromatic ring is contained in the structure.
• the crystalline polyester polyol (a1) is made of hexanediol as a raw material.
• the crystalline polyester polyol obtained by using hexanediol as a raw material has excellent crystallinity, and can express a certain hardness or more immediately after the moisture-curable polyurethane hot melt resin composition is applied, so that an excellent solidification rate, Appearance uniformity (suppressing bubbles and obtaining a film having a uniform surface appearance even when applied to an underlying substrate having irregularities. The same applies hereinafter), and adhesiveness (having excellent peel strength) The same shall apply hereinafter).
• crystalline means that a peak of crystallization heat or heat of fusion can be confirmed in DSC (differential scanning calorimeter) measurement in accordance with JIS K7121:2012, and "crystalline". Indicates that the peak cannot be confirmed.
• crystalline polyester polyol (a1) specifically, for example, a reaction product of hexanediol and a polybasic acid can be used.
• hexanediol examples include 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,4-hexanediol, 1,6-hexanediol and the like can be used. These compounds may be used alone or in combination of two or more. Among these, 1,6-hexanediol is preferably used because good crystallinity is obtained.
• polybasic acid examples include succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedicarboxylic acid, eicosadioic acid, citraconic acid, itaconic acid, citraconic anhydride, and anhydrous. Itaconic acid or the like can be used. These compounds may be used alone or in combination of two or more. Among these, it is preferable to use one or more compounds selected from the group consisting of adipic acid, sebacic acid, and dodecanedicarboxylic acid from the viewpoint of obtaining good crystallinity.
• the number average molecular weight of the crystalline polyester polyol (a1) is preferably in the range of 500 to 100,000, from the viewpoint of further excellent solidification rate, uniformity of appearance and adhesiveness. The range of ⁇ 50,000 is more preferred, and the range of 800 ⁇ 10,000 is more preferred.
• the number average molecular weight of the crystalline polyester polyol (a1) is a value measured by gel permeation chromatography (GPC) method.
• the content of the crystalline polyester polyol (a1) in the polyol (A) is 20% by mass or more from the viewpoint of further excellent flexibility, abrasion resistance, and flexibility.
• the range of 20 to 60% by mass is more preferable, and the range of 20 to 40% by mass is further preferable.
• polyol (A) in addition to the crystalline polyester polyol (a1), other polyols may be used in combination in consideration of other physical properties.
• polyether polyol (a2), other polyester polyol (a3) other than the crystalline polyester polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, dimer diol and the like can be used.
• These polyols may be used alone or in combination of two or more.
• polyether polyol (a2) examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropyran glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol and the like. Can be used. These polyether polyols may be used alone or in combination of two or more kinds. Among these, polypropylene glycol and/or polytetramethylene glycol are preferably used, and polytetramethylene glycol is more preferable, from the viewpoint that more excellent flexibility and flexibility can be obtained.
• the number average molecular weight of the polyether polyol (a2) is preferably in the range of 500 to 100,000, and more preferably 700 to 10,000, from the viewpoint of obtaining more excellent flexibility and flexibility. The range is more preferable, and the range of 8-00 to 5,000 is even more preferable.
• the number average molecular weight of the polyether polyol (a2) is a value measured by a gel permeation chromatography (GPC) method.
• the content of the polyether polyol (a2) in the polyol (A) is from 30 to 30 in terms of further excellent flexibility and flexibility.
• the amount is preferably 70% by mass, more preferably 30 to 50% by mass.
• polyester polyol (a3) it is preferable that it is not crystalline and does not have an alicyclic structure, from the viewpoint of obtaining further flexibility and flexibility, for example, having a hydroxyl group.
• a reaction product of a compound and a polybasic acid can be used.
• Examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, 2-methyl-1,8- Octanediol, 2,2-diethyl-1,3-propanediol, 2,2-diethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-diethyl-1 ,5 pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol; bisphenol A, bisphenol F, and alkylene oxide adducts thereof can be used.
• These compounds may be used alone or in combination of two or more.
• the range of /90 is preferable, and the range of 20/80 to 80/20 is more preferable.
• polybasic acid for example, succinic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, etc. can be used. These polybasic acids may be used alone or in combination of two or more.
• the number average molecular weight of the polyester polyol (a3) is preferably in the range of 500 to 100,000, and more preferably in the range of 700 to 10,000, from the viewpoint of obtaining more excellent flexibility and flexibility. Is more preferable, and the range of 8-00 to 5,000 is further preferable.
• the number average molecular weight of the polyester polyol (a3) is a value measured by gel permeation chromatography (GPC) method.
• the content of the polyether polyol (a3) in the polyol (A) is 10 to 50 from the viewpoint that more excellent flexibility and flexibility can be obtained. It is preferably in the range of mass% and more preferably in the range of 10 to 30 mass %.
• polyisocyanate (B) examples include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, cyclohexane.
• aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate and naphthalene diisocyanate; hexamethylene diisocyanate, cyclohexane.
• Aliphatic or alicyclic polyisocyanates such as diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferably used, and diphenylmethane diisocyanate is more preferable, from the viewpoint of obtaining excellent reactivity and adhesiveness.
• the amount of the polyisocyanate (B) used is preferably in the range of 5 to 40% by mass, and preferably in the range of 10 to 30% by mass based on the total mass of the raw materials constituting the hot melt urethane prepolymer (i). Is more preferable.
• the hot melt urethane prepolymer (i) is obtained by reacting the polyol (A) with the polyisocyanate (B), and is coated with an air- or moisture-curable polyurethane hot melt resin composition. It has an isocyanate group capable of reacting with the water present in the base material to form a crosslinked structure.
• the polyol (A) is placed in a reaction vessel containing the polyisocyanate (B), and the isocyanate group contained in the polyisocyanate (B) is It can be produced by reacting under an excessive condition with respect to the hydroxyl group of the polyol (A).
• the equivalent ratio (isocyanate group/hydroxyl group) between the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A) when producing the hot-melt urethane prepolymer (i) is further excellent.
• the range is preferably from 1.1 to 5, and more preferably from 1.5 to 3.
• the hot melt urethane prepolymer (i) obtained by the above method has an isocyanate group content (hereinafter, abbreviated as "NCO%") of 1.7, from the viewpoint of further excellent adhesiveness. It is preferably in the range of 5 to 5, more preferably in the range of 1.8 to 3.
• NCO% of the hot melt urethane prepolymer (i) is a value measured by a potentiometric titration method based on JISK1603-1:2007.
• the moisture-curable polyurethane hot melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may be used if necessary.
• additives examples include light resistance stability, curing catalyst, tackifier, plasticizer, stabilizer, filler, dye, pigment, optical brightener, silane coupling agent, wax, thermoplastic resin, etc. Can be used. These additives may be used alone or in combination of two or more.
• the synthetic leather of the present invention has a cured product layer of the moisture-curable polyurethane hot melt resin composition.
• the synthetic leather has, for example, at least a base material, an adhesive layer, and a skin layer.
• the base material examples include polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, and blends thereof.
• a fibrous base material such as a non-woven fabric, a woven fabric, or a knitted fabric made of fibers or the like; a non-woven fabric impregnated with a resin such as a polyurethane resin; ..
• the cured product layer of the moisture-curable polyurethane hot melt resin composition can form an adhesive layer and/or a skin layer.
• a material for forming a skin layer on a release paper is applied, and after forming a skin layer, a material for forming an adhesive layer is applied on the skin layer to form an adhesive layer.
• a material for forming an adhesive layer is applied on the skin layer to form an adhesive layer.
• the method include a method in which after forming the film, it is attached to a base material.
• an intermediate layer, a wet porous layer, and a surface treatment agent layer may be provided separately.
• a material other than the moisture-curable polyurethane hot melt resin composition is used for each layer, a known material can be used.
• the synthetic leather of the present invention is excellent in solidification speed, weather resistance, and uniformity of appearance, and can be particularly suitably used as split leather.
• the split leather includes a floor leather, an adhesive layer, and a skin layer, and the moisture-curable polyurethane hot melt resin composition can be suitably used as the adhesive layer of split leather.
• the moisture-curable polyurethane hot melt resin composition can be suitably used as the adhesive layer of split leather.
• a method for producing split leather when the moisture-curable polyurethane hot melt resin composition is used for the adhesive layer will be described.
• the floor leather known ones can be used, for example, natural leather such as cow, horse, sheep, goat, deer, kangaroo, etc., which is composed of a layer obtained by removing the epidermis and papillary layer. Can be used. It is preferable to use these floor leathers that have undergone a known leather manufacturing process, tanning process, and dyeing/finishing process.
• the thickness of the floor leather is appropriately determined according to the intended use, but is, for example, in the range of 0.1 to 2 mm.
• a method of forming the adhesive layer on the floor leather for example, a method of coating the moisture-curable polyurethane hot melt resin composition melted at 50 to 130° C. on the floor leather A method in which, for example, the moisture-curable polyurethane hot melt resin composition melted at 50 to 130° C. is coated on release paper, and then the cured product layer is attached to the floor leather; On the formed skin layer, for example, a method of applying the moisture-curable polyurethane hot melt resin composition melted at 50 to 130° C. and then laminating the cured material layer to the floor leather can be mentioned.
• a method for applying the moisture-curable polyurethane hot melt resin composition for example, a roll coater, a knife coater, a spray coater, a gravure coater, a comma coater, a T-die coater, an applicator or the like is used. There is a method.
• the moisture-curable polyurethane hot melt resin composition After applying the moisture-curable polyurethane hot melt resin composition, it can be dried and cured by a known method.
• the thickness of the cured product layer (adhesive layer) of the moisture-curable urethane hot melt resin composition is, for example, in the range of 5 to 300 ⁇ m.
• known resins can be used, for example, solvent-based urethane resin, water-based urethane resin, solvent-free urethane resin, solvent-based acrylic resin, water-based acrylic resin, etc. You can These resins may be used alone or in combination of two or more.
• a heating method for removing the solvent in the resin for forming the skin layer for example, a method of performing the heating at a temperature of 50 to 120° C. for 2 to 20 minutes can be mentioned.
• the thickness of the skin layer is, for example, in the range of 5 to 100 ⁇ m.
• Example 1 A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was reacted with crystalline polyester polyol (1,6-hexanediol and adipic acid, number average molecular weight; 2 5,000, hereinafter abbreviated as "crystalline PEs1") 150 parts by mass, polytetramethylene glycol (number average molecular weight; 1,000, hereinafter abbreviated as "PTMG”) 250 parts by mass, polyester polyol (1, A mixture of 6-hexanediol, neopentyl glycol, and adipic acid, number average molecular weight: 2,000, hereinafter abbreviated as "other PEs1".) 100 parts by mass were added, mixed, and depressurized at 100°C.
• crystalline PEs1 polytetramethylene glycol
• PTMG number average molecular weight
• other PEs1 A mixture of 6-hexan
• Examples 2-6, Comparative Examples 1-2 A urethane prepolymer and split leather were prepared in the same manner as in Example 1 except that the type and amount of the polyol (A) and the amount of the polyisocyanate (B) used were changed as shown in Tables 1 and 2. Obtained.
• the number average molecular weight of the polyols used in Examples and Comparative Examples is a value measured by the gel permeation chromatography (GPC) method under the following conditions.
• Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSK gel G4000” (7.8 mm ID x 30 cm) x 1 "TSK gel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (differential refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL/min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: A calibration curve was prepared using the following standard polystyrene.
• Crystall PEs2 a reaction product of 1,6-hexanediol and sebacic acid, number average molecular weight: 3500 "Crystalline PEs3"; 1,6-hexanediol and dodecanedicarboxylic acid reacted, number average molecular weight; 3700 "Other PEs2”; ethylene glycol, neopentyl glycol, 1,6-hexanediol, and adipic acid reacted, number average molecular weight; 5500 "Other PEs3”; 3-methyl-1,5-pentanediol and adipic acid reacted, number average molecular weight; 2000 “Aromatic PEs”; those obtained by reacting diethylene glycol, neopentyl glycol, and phthalic anhydride, number average molecular weight; 975
• Examples 1 to 6 which are the synthetic leathers of the present invention, are excellent in solidification rate, weather resistance, appearance uniformity, and toughness.
• Comparative Example 1 was a mode in which the crystalline polyester polyol (a1) made from hexanediol was not used, but the solidification rate and the uniformity of appearance were poor.
• Comparative Example 2 is an embodiment using the aromatic polyester polyol (a1), but was poor in weather resistance and flexibility.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Textile Engineering (AREA)
• Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
• Polyurethanes Or Polyureas (AREA)

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• 2019
  • 2019-12-03 WO PCT/JP2019/047145 patent/WO2020129603A1/ja active Application Filing
  • 2019-12-03 KR KR1020217013556A patent/KR102614433B1/ko active IP Right Grant
  • 2019-12-03 JP JP2020544876A patent/JP6844756B2/ja active Active
  • 2019-12-03 CN CN201980081380.7A patent/CN113195825B/zh active Active
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