WO2019082475A1 - Composition de résine uréthane, film de revêtement et cuir synthétique - Google Patents

Composition de résine uréthane, film de revêtement et cuir synthétique

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Publication number
WO2019082475A1
WO2019082475A1 PCT/JP2018/029888 JP2018029888W WO2019082475A1 WO 2019082475 A1 WO2019082475 A1 WO 2019082475A1 JP 2018029888 W JP2018029888 W JP 2018029888W WO 2019082475 A1 WO2019082475 A1 WO 2019082475A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
parts
urethane resin
resin composition
glycol
Prior art date
Application number
PCT/JP2018/029888
Other languages
English (en)
Japanese (ja)
Inventor
宏之 千々和
保之 片上
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2018558260A priority Critical patent/JP6528915B1/ja
Publication of WO2019082475A1 publication Critical patent/WO2019082475A1/fr

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Classifications

    • 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
    • C08G18/44—Polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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

Definitions

  • the present invention relates to a urethane resin composition.
  • Urethane resin is widely used in various fields such as synthetic leather and sheets for molding processing. However, higher durability is required particularly when used for long-term members such as synthetic leather for vehicle interior materials.
  • the above-mentioned evaluation items of durability are various and include heat resistance, moist heat resistance, light resistance, chemical resistance, abrasion resistance and the like, and in particular, in recent years, synthetic leather members frequently in contact with the human body.
  • chemical resistance such as oleic acid resistance and sun oil resistance.
  • a resin composition comprising a polycarbonate-based polyurethane resin, a polyether-based polyurethane resin, and an acrylic resin is disclosed (see, for example, Patent Document 1).
  • the problem to be solved by the present invention is to provide a urethane resin composition excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
  • the present invention provides polycarbonate polyols (A) starting from butanediol and hexanediol, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-). 3) A polyol (X) containing at least one glycol compound (B) selected from the group consisting of 3), and a urethane resin (Z) containing polyisocyanate (Y) as an essential raw material It is intended to provide a urethane resin composition.
  • Another object of the present invention is to provide a film formed of the above urethane resin composition, and a synthetic leather characterized by having the film.
  • the urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
  • the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.
  • the urethane resin composition of the present invention comprises a polycarbonate polyol (A) using butanediol and hexanediol as raw materials, a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aroma
  • the polycarbonate polyol (A) is essential to use butanediol and hexanediol as raw materials.
  • butanediol for example, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol and the like can be used. These butanediols may be used alone or in combination of two or more. Among these, 1,4-butanediol is preferably used from the viewpoint of obtaining further excellent mechanical strength.
  • hexanediol examples include 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, and 2,3-hexanediol. 2,4-hexanediol, 3,4-hexanediol and the like can be used. These hexanediols may be used alone or in combination of two or more. Among these, it is preferable to use 1,6-hexanediol from the viewpoint of obtaining a further excellent mechanical strength.
  • the molar ratio [C4 / C6] of the butanediol (C4) and the hexanediol diol (C6) is in the range of 60/40 to 95/5 from the viewpoint of obtaining even more excellent mechanical strength. It is preferably in the range of 65/35 to 93/7.
  • polycarbonate diol (A) specifically, one obtained by reacting the butanediol and hexanediol with a carbonate and / or phosgene according to a known method can be used.
  • dimethyl carbonate diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate etc.
  • carbonate dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, propylene carbonate etc.
  • these compounds may be used alone or in combination of two or more.
  • the number average molecular weight of the polycarbonate diol (A) is preferably in the range of 1,500 to 3,500, from the viewpoint of obtaining even more excellent mechanical strength.
  • the number average molecular weight of the polycarbonate polyol (A) is a value measured by gel permeation chromatography (GPC).
  • the amount of the polycarbonate polyol (A) used is preferably 30% by mass or more in the polyol (X), from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength.
  • the range of -99% by mass is more preferable, and the range of 50-95% by mass is more preferable.
  • the polyol (X) to be used in the present invention is selected from the group consisting of a monocyclic aliphatic glycol (b-1), a glycol having a spiro ring (b-2), and an aromatic glycol (b-3) It is essential to use a glycol compound (B) of a kind or more.
  • a glycol compound (B) of a kind or more.
  • the monocyclic aliphatic glycol (b-1) for example, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, alkylene oxide adducts of these, etc. can be used. These glycols may be used alone or in combination of two or more. Among these, cyclohexane dimethanol, hydrogenated bisphenol A, and an alkylene oxide adduct of hydrogenated bisphenol A are selected from the viewpoint that oleic acid resistance, low temperature flexibility and mechanical strength can be further improved. Preferably, one or more glycols are used.
  • glycol (b-2) having a spiro ring for example, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] Undecane, 3,9-bis (2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (1-methyl-2-hydroxyethyl) -2, 4,8,10-Tetraoxaspiro [5,5] undecane, 3,9-bis (1-ethyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-Bis (1-ethyl-1-methyl-2-hydroxyethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis (2-hydroxyethyl-2) -Methyl) -2,4,8 10-t
  • glycols may be used alone or in combination of two or more.
  • aromatic glycol for example, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydroquinone, and alkylene oxide adducts thereof may be used. it can. These glycols may be used alone or in combination of two or more.
  • the content of the glycol compound (B) is preferably less than 10% by mass in the polyol (X) from the viewpoint of obtaining even more excellent oleic acid resistance, low temperature flexibility and mechanical strength.
  • the range of ⁇ 9 mass% is more preferable, and the range of 2 ⁇ 7 mass% is more preferable.
  • the said polyol (X) contains the said polycarbonate polyol (A) and the said glycol compound (B) as an essential component, you may further contain other polyols as needed.
  • polycarbonate polyol other than said (A) polyether polyol, polyester polyol, polyacryl polyol, a polybutadiene polyol, a hydrogenated polybutadiene polyol etc.
  • polyether polyol polyether polyol
  • polyester polyol polyacryl polyol
  • polybutadiene polyol polybutadiene polyol
  • hydrogenated polybutadiene polyol etc.
  • polyols may be used alone or in combination of two or more.
  • polycarbonate polyols other than the above (A) can be used from the viewpoint that even more excellent oleic acid resistance, low temperature flexibility and mechanical strength can be obtained by using in combination with the polycarbonate polyol (A). preferable.
  • the polycarbonate polyols other than the above (A) are not particularly limited as long as they have a carbonate structure, but, for example, propanediol, butanediol, pentanediol, hexanediol, decanediol, caprolactone, cyclohexanedimethanol, 3-methyl-1
  • Polycarbonate polyols and the like can be used which are starting materials such as 3,5-pentanediol, neopentyl glycol and isosorbide. These raw materials may be used alone as a raw material having a hydroxyl group or in combination of two or more.
  • the amount used when using polycarbonate polyols other than the above (A) is less than 40% by mass in the polyol (X) from the viewpoint of obtaining more excellent oleic acid resistance, low temperature flexibility and mechanical strength.
  • the range of 1 to 35% by mass is more preferable, and the range of 3 to 33% by mass is even more preferable.
  • chain extenders having a number average molecular weight of 40 to 550 may be used in combination with the polyol (X).
  • Examples of the other chain extender include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, and trimethylolpropane.
  • a chain extender having a hydroxyl group such as glycerin; ethylene diamine, 1,2-propane diamine, 1,6-hexamethylene diamine, piperazine, 2-methyl piperazine, 2,5-dimethyl piperazine, isophorone diamine, 4,4'- Dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, 1,2-cyclohexanediamine, 1,4-cyclohexanediamine, aminoethyl ethanolamine, hydrazine, diethylene Riamin, can be used a chain extender having an amino group such as triethylene tetramine.
  • These chain extenders may be used alone or in combination of two or more. Among these, it is preferable to use a chain extender having an amino group, and it is more preferable to use a chain extender having an amino group and an alicyclic structure, from the viewpoint of easily suppressing the discoloration of the film over time.
  • the amount of use in the case of using the other chain extender is preferably in the range of 1 to 50 parts by mass with respect to 100 parts by mass of the polyol (X) from the viewpoint of easily suppressing discoloration of the film over time.
  • the range of 3 to 20 parts by mass is more preferable.
  • polyisocyanate (Y) for example, 1,3- and 1,4-phenylene diisocyanate, 1-methyl-2,4-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-2, 5-phenylene diisocyanate, 1-methyl-2,6-phenylene diisocyanate, 1-methyl-3,5-phenylene diisocyanate, 1-ethyl-2,4-phenylene diisocyanate, 1-isopropyl-2,4-phenylene diisocyanate, 1 , 3-Dimethyl-2,4-phenylene diisocyanate, 1,3-dimethyl-4,6-phenylene diisocyanate, 1,4-dimethyl-2,5-phenylene diisocyanate, diethylbenzene diisocyanate, diisopropylbenzene diisocyanate 1-Methyl-3,5-diethylbenzene diisocyanate, 3-methyl-1,5-diethy
  • polyisocyanates may be used alone or in combination of two or more.
  • aliphatic and / or alicyclic polyisocyanates are preferably used from the viewpoint of obtaining further excellent durability and improving light resistance, oleic acid resistance, and low temperature flexibility. It is preferable to use an aliphatic polyisocyanate and a cycloaliphatic polyisocyanate in combination.
  • the mass ratio [aliphatic NCO / alicyclic NCO] is preferably in the range of 5/95 to 60/40, more preferably in the range of 10/90 to 50/50, and more preferably 15/85 to 45 /. A range of 55 is more preferred.
  • the amount of the polyisocyanate (Y) used is in the range of 10 to 60% by mass in the total mass of the polyol (X) and the polyisocyanate (Y), from the viewpoint of obtaining excellent mechanical strength and reactivity. Is preferable, and the range of 15 to 45% by mass is more preferable.
  • Examples of the method for producing the urethane resin (Z) include a method in which the polyol (X) and the polyisocyanate (Y) are charged at one time and reacted, and the reaction is carried out, for example, It is preferable to carry out at a temperature of 100 ° C. for 3 to 10 hours. Also, the reaction may be carried out in a solvent described later.
  • the molar ratio [(isocyanate group) / (hydroxy group and amino group)] between the hydroxyl group of the polyol (X) and the isocyanate group of the polyisocyanate (Y) is in the range of 0.6 to 2. Preferably, it is more preferably in the range of 0.8 to 1.2.
  • the number average molecular weight of the urethane resin (Z) obtained by the above method is preferably in the range of 5,000 to 1,000,000 in that the mechanical strength and flexibility of the film can be further improved.
  • the range of 10,000 to 500,000 is more preferable.
  • the number average molecular weight of the said urethane resin (Z) shows the value measured by gel permeation chromatography (GPC) method.
  • the said urethane resin composition contains the said urethane resin (Z) as an essential component, you may contain another component as needed.
  • Examples of the other components include solvents, pigments, flame retardants, plasticizers, softeners, stabilizers, waxes, antifoaming agents, dispersants, penetrants, surfactants, fillers, mildewproofing agents, antibacterial agents,
  • a UV absorber, an antioxidant, a weathering stabilizer, a fluorescent whitening agent, an antiaging agent, a thickener and the like can be used. These components may be used alone or in combination of two or more.
  • the solvent examples include ketone solvents such as water, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, methyl-n-propyl ketone, acetone and methyl isobutyl ketone; Ester solvents such as methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, ethyl acetate, isopropyl acetate, isobutyl acetate, isobutyl acetate and sec-butyl acetate; alcohol solvents such as methanol, ethanol, isopropyl alcohol and butanol can be used . These solvents may be used alone or in combination of two or more.
  • ketone solvents such as water, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone,
  • the content of the solvent is preferably in the range of 30 to 90% by mass in the urethane resin composition from the viewpoint of workability and viscosity.
  • the urethane resin composition of the present invention is coated on a substrate and dried to obtain a film.
  • the fibrous base material which consists of a nonwoven fabric, woven fabric, knitting etc., resin film etc.
  • the fibrous base material include chemical fibers such as polyester fiber, nylon fiber, acrylic fiber, polyurethane fiber, acetate fiber, rayon fiber, polylactic acid fiber, etc .; cotton, hemp, silk, wool, etc. Blended fibers can be used.
  • the resin film for example, a polyethylene terephthalate film, a polycarbonate film, an acrylic resin film, a COP (cycloolefin polymer) film, a TAC (triacetyl cellulose) film or the like can be used.
  • the surface of the substrate may be subjected to treatments such as antistatic treatment, mold release treatment, water repellent treatment, water absorption treatment, antibacterial deodorizing treatment, antibacterial treatment, ultraviolet blocking treatment, etc., as necessary. .
  • Examples of a method of applying the urethane resin composition of the present invention to the substrate include a coating method using an applicator, a bar coater, a knife coater, a T-die coater, a roll coater or the like.
  • Examples of the method of drying the applied urethane resin composition include a method of drying at a temperature of 50 to 140 ° C. for 30 seconds to 10 minutes.
  • the thickness of the resulting film is appropriately determined in accordance with the application to be used, and is, for example, in the range of 0.001 to 10 mm.
  • the 100% modulus obtained by the tensile test at a crosshead speed of 10 mm / sec is 9 MPa, from the viewpoint that even better abrasion resistance can be obtained.
  • the above is preferable, and the range of 11 to 20 MPa is more preferable.
  • the measuring method of the said 100% modulus value of the said film is described in the Example.
  • the film In order to obtain a synthetic leather using the film, it is preferable to use the film as the skin layer or top coat layer of the synthetic leather.
  • Examples of the method for producing the synthetic leather include a method of bonding the surface treatment layer formed on a release paper and the film by a known method.
  • a material which forms the said surface treatment layer solvent-type urethane resin, water-based urethane resin, water-based acrylic resin etc. can be used, for example.
  • the urethane resin composition of the present invention is excellent in oleic acid resistance, low temperature flexibility, and mechanical strength. Therefore, the urethane resin composition of the present invention can be suitably used as a material used for producing synthetic leather, clothing, support pads, polishing pads and the like, and particularly preferably used as a material of synthetic leather it can.
  • Example 1 A polycarbonate diol (having 1,4-butanediol and 1,6-hexanediol as a raw material, [C4 / C6] (hereinafter, referred to as “C4 / C6”), was added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer.
  • IPDA isophorone diamine
  • Example 2 117 parts by mass of PC1 and 8 parts by mass of other PC1 were added to a nitrogen-replaced four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. . After dehydration, 97 parts by mass of DMF and 5 parts by mass of cyclohexanedimethanol (hereinafter abbreviated as “CHDM”) were added while cooling to 50 ° C., and the mixture was sufficiently stirred.
  • CHDM cyclohexanedimethanol
  • PC2 Number average molecular weight: 2,000
  • H12MDI 4,4'-dicyclohexylmethane diisocyanate
  • Example 5 102 parts by mass of PC1 and 29 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 98 parts by mass of DMF and 5 parts by mass of SPG were added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 39 parts by mass of IPDI, and 7 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C.
  • Comparative Example 1 109 parts by mass of PC2 and 26 parts by mass of other PC1 were added to a nitrogen-replaced four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C under a reduced pressure of 0.095 MPa. . After dehydration, while cooling to 50 ° C., 100 parts by mass of DMF and 1 part by mass of ethylene glycol (hereinafter abbreviated as “EG”) were added and sufficiently stirred.
  • EG ethylene glycol
  • Comparative Example 2 88 parts by mass of PC2 and 59 parts by mass of other PC1 were added to a nitrogen-substituted four-necked flask having a stirrer, a reflux condenser and a thermometer, and dehydration was performed at 120 to 130 ° C. under a reduced pressure of 0.095 MPa. . After dehydration, 101 parts by mass of DMF was added while cooling to 50 ° C., and the mixture was sufficiently stirred. After stirring, 34 parts by mass of IPDI, and 6 parts by mass of HDI and 0.1 parts by mass of stannous octoate are added, and reacted at 75 ° C.
  • the number average molecular weights of the polyol and the like used in Examples and Comparative Examples are values measured under the following conditions by gel permeation chromatography (GPC).
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were used in series connection. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 This "TSKgel G2000" (7.8 mm ID ⁇ 30 cm) ⁇ 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.
  • the sample was pulled at a head speed of 10 mm / sec, and the 100% modulus (MPa) of the test piece was measured. The distance between chucks at this time was 40 mm. From the obtained 100% modulus value, mechanical strength was evaluated as follows. "A”: 11 MPa or more and less than 20 MPa "B”: 9 MPa or more and less than 11 MPa "C”: less than 9 MPa
  • a film was produced in the same manner as the above-mentioned [Method of measuring mechanical strength]. Subsequently, the film was cut into strips of 5 mm in width and 50 mm in length, immersed in oleic acid at normal temperature for 24 hours and then taken out, and oleic acid adhering to the surface was lightly wiped off with a paper waste. Then, using a tensile tester “Autograph AG-I” (manufactured by Shimadzu Corporation), the specimen is pulled under the conditions of a crosshead speed of 10 mm / sec and a chuck distance of 40 mm under an atmosphere of temperature 23 ° C. The stress at 100% elongation was measured.
  • the oleic acid resistance was evaluated as follows using the value obtained by dividing this stress by the 100% modulus value measured in the above-mentioned [Method for measuring mechanical strength] as the retention of the 100% modulus value. "A”: retention rate is 40% or more "B”: retention rate is 30% or more and less than 40% “C”: retention rate is less than 30%
  • This synthetic leather is subjected to a flexibility test (-10 ° C, 100 times / minute) with a flexometer (“low temperature bath-equipped flexiometer” manufactured by Yasuda Seiki Co., Ltd.) until the surface of the synthetic leather is cracked The number of times was measured and evaluated as follows. "A”: 20,000 or more "B”: 10,000 or more and less than 20,000 "C”: less than 10,000
  • Examples 1 to 6 which are the urethane resin compositions of the present invention, were found to be excellent in oleic acid resistance, low temperature flexibility, and mechanical strength.
  • Comparative Example 1 was an embodiment in which ethylene glycol was used instead of the glycol compound (B), but oleic acid resistance was poor.
  • the comparative example 2 is an aspect which does not use a glycol compound (B) and its substitute, either, mechanical strength and oleic acid resistance were inferior.

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

Abstract

Le problème à résoudre par la présente invention est de fournir une composition de résine uréthane qui présente d'excellentes propriétés de résistance à l'acide oléique, de flexibilité à basse température et de résistance mécanique. La présente invention concerne une composition de résine uréthane caractérisée en ce qu'elle contient : (Y) un polyisocyanate ; et (Z) une résine uréthane obtenue en utilisant, comme matières premières essentielles, (X) un polyol qui contient (A), un polycarbonate polyol obtenu en utilisant du butanediol et de l'hexanediol comme matières premières, et (B) au moins un type de composé glycol choisi dans le groupe constitué par un glycol aliphatique monocyclique (b-1), un glycol contenant un noyau spiro (b-2), et un glycol aromatique (b3). La présente invention concerne également : un film de revêtement caractérisé en ce qu'il est formé à partir de la composition de résine uréthane ; et un cuir synthétique caractérisé en ce qu'il comprend le film de revêtement.
PCT/JP2018/029888 2017-10-27 2018-08-09 Composition de résine uréthane, film de revêtement et cuir synthétique WO2019082475A1 (fr)

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CN114507330B (zh) * 2022-01-06 2024-02-23 四川东树新材料有限公司 聚氨酯组合物

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