WO2023013510A1 - Résine de polyuréthane et son procédé de production - Google Patents

Résine de polyuréthane et son procédé de production Download PDF

Info

Publication number
WO2023013510A1
WO2023013510A1 PCT/JP2022/029044 JP2022029044W WO2023013510A1 WO 2023013510 A1 WO2023013510 A1 WO 2023013510A1 JP 2022029044 W JP2022029044 W JP 2022029044W WO 2023013510 A1 WO2023013510 A1 WO 2023013510A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane resin
polycarbonate polyol
polyether polycarbonate
structural units
cyclic ether
Prior art date
Application number
PCT/JP2022/029044
Other languages
English (en)
Japanese (ja)
Inventor
豊一 鈴木
省吾 藤▲崎▼
Original Assignee
Ａｇｃ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 Ａｇｃ株式会社 filed Critical Ａｇｃ株式会社
Priority to JP2023540295A priority Critical patent/JPWO2023013510A1/ja
Publication of WO2023013510A1 publication Critical patent/WO2023013510A1/fr

Links

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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • 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
    • 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 polyurethane resin and a method for producing the same.
  • Polycarbonate polyurethane resin is known as a raw material for synthetic leather used for shoes, bags, clothing, furniture, vehicle seats, chair upholstery, etc., and has oleic acid resistance, flexibility, and A balance of durability is required.
  • Synthetic leather can be obtained, for example, by applying a polyurethane resin solution to a fibrous base material or a film-forming plate and solidifying it in water.
  • Patent Literature 1 discloses a polyurethane resin comprising a polymeric diol, an organic isocyanate and, if necessary, a chain extender.
  • Patent Document 2 discloses a polyurethane (A) composed of a polycarbonate diol, an organic diisocyanate and a low-molecular-weight diol, and a polyester-based diol obtained from a diol having a specific structure and a dicarboxylic acid, an organic diisocyanate and a low-molecular-weight diol.
  • a polyurethane composition comprising polyurethane (B) is disclosed.
  • the object of the present invention is to solve such problems, and to provide a polyurethane resin excellent in oleic acid resistance, flexibility, and hydrolysis resistance, and a method for producing the same.
  • the present invention is as follows.
  • a polyurethane resin having structural units derived from a polyether polycarbonate polyol and structural units derived from a polyisocyanate compound has a structural unit derived from an initiator, a structural unit derived from a cyclic ether, and a structural unit derived from carbon dioxide,
  • the initiator has an active hydrogen-containing group and has 3.0 or less structural units derived from a cyclic ether per molecule
  • the polyether polycarbonate polyol is a polyurethane resin in which the average chain number of structural units derived from a cyclic ether is 1.0 or more and 3.0 or less.
  • the structural unit derived from the cyclic ether contained in the polyether polycarbonate polyol is at least one structural unit selected from the group consisting of structural units derived from ethylene oxide and structural units derived from propylene oxide. , the polyurethane resin according to any one of the above [1] to [7]. [9] The polyurethane resin according to any one of [1] to [8] above, wherein the polyisocyanate compound is a diisocyanate compound. [10] The polyurethane resin according to any one of [1] to [9] above, further comprising a structural unit derived from a chain extender.
  • the term "unit" constituting a polymer means an atomic group formed by polymerization of monomers.
  • the hydroxyl value equivalent molecular weight of the polyether polycarbonate polyol is the hydroxyl value calculated based on JIS K 1557 (2007), [56,100 / (hydroxyl value)] ⁇ (number of functional groups) formula It is a molecular weight calculated using the value obtained by applying to.
  • the number average molecular weight (hereinafter sometimes referred to as "Mn") of the polyurethane resin, and the Mn and weight average molecular weight (hereinafter sometimes referred to as "Mw") of the polyether polycarbonate polyol are using gel permeation chromatography (GPC) according to the method described in 1, and using a standard polystyrene sample with a known molecular weight to prepare a calibration curve and measure the molecular weight in terms of polystyrene.
  • the molecular weight distribution is a value calculated from the above Mw and Mn, and is the ratio of Mw to Mn (hereinafter sometimes referred to as "Mw/Mn").
  • the polyurethane resin of the present invention is a polyurethane resin having a structural unit derived from a polyether polycarbonate polyol and a structural unit derived from a polyisocyanate compound
  • the polyether polycarbonate polyol has a structural unit derived from an initiator, a structural unit derived from a cyclic ether, and a structural unit derived from carbon dioxide
  • the initiator has an active hydrogen-containing group and has 3.0 or less structural units derived from a cyclic ether per molecule
  • the polyether polycarbonate polyol has an average chain number of structural units derived from cyclic ether of 1.0 or more and 3.0 or less.
  • the polyurethane resin of the present invention has structural units derived from a polyether polycarbonate polyol having a specific structure and structural units derived from a polyisocyanate compound, thereby improving oleic acid resistance, flexibility, and hydrolysis resistance. Excellent.
  • polyether polycarbonate polyol has structural units derived from an initiator having a specific structure, structural units derived from a cyclic ether having a specific structure, and structural units derived from carbon dioxide.
  • the average chain number of structural units derived from cyclic ether (hereinafter also referred to as AO—AO average chain number) is 1.0 or more and 3.0 or less. If the AO—AO average chain number is less than 1.0, the flexibility may decrease, and if it exceeds 3.0, the oleic acid resistance of the resulting polyurethane resin may decrease. From such a viewpoint, the AO-AO average chain number is preferably 1.2 or more and 2.9 or less, more preferably 1.3 or more and 2.8 or less, and still more preferably 1.4 or more and 2 .7 or less.
  • the AO—AO average chain number can be adjusted to 1.0 or more and 3.0 or less by appropriately adjusting the ratio of structural units derived from carbon dioxide in the polyether polycarbonate polyol.
  • the AO-AO average chain number can be calculated from the following formula (1). Specifically, it can be measured by the method described in Examples.
  • AO-AO average chain number (number of molecules of structural unit derived from cyclic ether) / (number of molecules of structural unit derived from carbon dioxide + 1) (1)
  • the number of molecules of the structural unit derived from the cyclic ether is calculated from the hydroxyl value-equivalent molecular weight of the polyether polycarbonate polyol and the ratio of the structural units derived from the cyclic ether calculated from 1 H-NMR.
  • the number of molecules of structural units derived from carbon dioxide is calculated from the hydroxyl value-equivalent molecular weight of the polyether polycarbonate polyol and the proportion of structural units derived from carbon dioxide calculated from 1 H-NMR.
  • the hydroxyl value-equivalent molecular weight of the polyether polycarbonate polyol is preferably 700 to 10,000, more preferably 800 to 8,000, still more preferably 850 to 6,000, still more preferably 900 to 3,000.
  • the obtained polyurethane resin has better flexibility
  • the hydroxyl value-equivalent molecular weight is 10,000 or less
  • the obtained polyurethane resin has better strength.
  • the hydroxyl value-equivalent molecular weight is measured by the method described in Examples below.
  • the number average molecular weight (Mn) of the polyether polycarbonate polyol is preferably 700 to 10,000, more preferably 800 to 8,000, even more preferably 850 to 6,000, and still more preferably 900 to 3,000.
  • the molecular weight distribution (Mw/Mn) which is represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), of the polyether polycarbonate polyol is from the viewpoint of improving the flexibility and strength of the resulting polyurethane resin.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mw/Mn molecular weight distribution
  • the proportion of structural units derived from carbon dioxide in the polyether polycarbonate polyol is preferably 10 to 30% by mass, more preferably 12 to 28% by mass, and still more preferably 13 to 27% by mass.
  • the ratio of structural units derived from carbon dioxide is measured by the method described in Examples below.
  • a structural unit in which a structural unit derived from carbon dioxide, a structural unit derived from a cyclic ether, and a structural unit derived from carbon dioxide in the polyether polycarbonate polyol are chained in this order (hereinafter, also referred to as a CO 2 —AO—CO 2 chain ) is preferably 3% by mass or more, more preferably 4% by mass or more, and still more preferably 5% by mass or more, from the viewpoint of improving the oleic acid resistance of the polyurethane resin. From the viewpoint of better flexibility of the polyurethane resin, the content is preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less.
  • polyether polycarbonate polyol structural units derived from a cyclic ether, structural units derived from a cyclic ether, and structural units in which structural units derived from a cyclic ether are linked in this order (hereinafter also referred to as an AO-AO-AO chain)
  • the proportion is preferably from 38 to 70% by mass, more preferably from 40 to 68% by mass, and even more preferably from 43 to 65% by mass, from the viewpoint of better oleic acid resistance of the polyurethane resin.
  • a structural unit in which a structural unit derived from a cyclic ether, a structural unit derived from a cyclic ether, and a structural unit derived from carbon dioxide in the polyether polycarbonate polyol are chained in this order (hereinafter also referred to as AO-AO-CO 2 chain) is preferably from 12 to 59% by mass, more preferably from 15 to 56% by mass, and even more preferably from 17 to 52% by mass, from the viewpoint of better oleic acid resistance of the polyurethane resin.
  • the ratio of CO 2 —AO—CO 2 chains, the ratio of AO—AO—AO chains, and the ratio of AO—AO—CO 2 chains in the polyether polycarbonate polyol are, for example, when the cyclic ether AO is propylene oxide PO.
  • the polyether polycarbonate polyol is dissolved in deuterated chloroform to 10% by mass, and 1 H-NMR is measured with an NMR device with a resolution of 400 MHz.
  • the area of the 3H peak (1.34 ppm) derived from the methyl group of propylene oxide PO as the cyclic ether AO flanked by carbonate on both ends, one for CO and the other for the methyl group of PO flanked by PO It can be calculated based on the area of the derived 3H peak (1.29 ppm) and the area of the methyl group derived 3H peak (1.14 ppm) of PO flanked by PO on both ends. Specifically, it can be measured by the method described in Examples.
  • the total content of structural units derived from an initiator having a specific structure, structural units derived from a cyclic ether having a specific structure, and structural units derived from carbon dioxide in the polyether polycarbonate polyol is not particularly limited. However, it is preferably 80% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 100% by mass (a structural unit derived from an initiator having a specific structure, It may consist only of a structural unit derived from a cyclic ether having a specific structure and a structural unit derived from carbon dioxide).
  • the initiator has an active hydrogen-containing group.
  • the active hydrogen-containing group include a hydroxyl group, a carboxy group, and an amino group having a hydrogen atom bonded to a nitrogen atom.
  • the active hydrogen-containing group of the initiator is preferably a hydroxyl group.
  • the initiator preferably has 2 to 8 active hydrogen-containing groups, more preferably 2 to 6 groups, and even more preferably 2 to 4 groups.
  • the initiator has 3.0 or less structural units derived from a cyclic ether per molecule. If the number of constitutional units derived from cyclic ether per molecule exceeds 3.0, the obtained polyurethane resin may have lower oleic acid resistance. From such a viewpoint, the number of structural units derived from cyclic ether per molecule is preferably 2.5 or less, more preferably 2.0 or less, and may be 0.0.
  • the initiator may be a polyol that does not have structural units derived from cyclic ethers.
  • the structural unit derived from the cyclic ether may be a structural unit derived from ethylene oxide or propylene oxide from the viewpoint of better flexibility and strength of the polyurethane resin. derived structural units are preferred.
  • the initiator preferably has a molecular weight of 40 to 3,000, more preferably 40 to 2,000, still more preferably 55 to 2,000, and even more preferably 60 to 1,500. .
  • the molecular weight is a hydroxyl value-equivalent molecular weight or a value calculated from a molecular formula.
  • the initiator preferably has 2 to 8 active hydrogen-containing groups and a molecular weight of 40 to 3,000, and preferably has 2 to 4 active hydrogen-containing groups and a molecular weight of 60 to 1,500. is more preferred.
  • the initiator examples include polyols, polyhydric phenols, polyhydric carboxylic acids, and amine compounds having two or more hydrogen atoms bonded to nitrogen atoms.
  • the initiator is preferably a polyol having 2 to 8 hydroxyl groups, more preferably a polyol having 2 to 6 hydroxyl groups.
  • the number of carbon atoms in the initiator is preferably a polyol having 2 to 20 carbon atoms, more preferably a polyol having 2 to 12 carbon atoms, from the viewpoint of good oleic acid resistance of the resulting polyurethane resin.
  • the initiator is preferably a polyol having 2 to 8 hydroxyl groups and 2 to 12 carbon atoms, more preferably a diol having 2 to 12 carbon atoms.
  • polyols as initiators include ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, polyoxyalkylenediol with a molecular weight of 40 to 3000, poly with a molecular weight of 200 to 3000 Oxyalkylene triols, polycarbonate diols having a molecular weight of 300-3000 and polycarbonate triols having a molecular weight of 300-3000 can be mentioned.
  • Polyols as initiators include ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8 - Octanediol, glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol are preferred, ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octanediol are more preferred.
  • the cyclic ether constituting the structural unit derived from the cyclic ether of the polyether polycarbonate polyol is not particularly limited as long as the AO-AO average chain number in the polyether polycarbonate polyol satisfies 1.0 or more and 3.0 or less.
  • the number of carbon atoms forming the ring of the cyclic ether is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4.
  • a carbon atom forming a ring of the cyclic ether may have a substituent, and examples of the substituent include an alkyl group having 1 to 4 carbon atoms, a halogen atom, a hydroxyl group, and the like.
  • cyclic ether examples include rings of ethylene oxide (hereinafter sometimes referred to as "EO”), propylene oxide (hereinafter sometimes referred to as “PO”), 1,2-butylene oxide, 2,3-butylene oxide, and the like. Cyclic ethers formed with two carbon atoms can be mentioned. These may be used individually by 1 type, and may be used 2 or more types.
  • the structural unit derived from the cyclic ether contained in the polyether polycarbonate polyol is a group consisting of structural units derived from ethylene oxide and structural units derived from propylene oxide, from the viewpoint of better flexibility and strength of the polyurethane resin. It is preferably at least one more selected structural unit, more preferably a structural unit derived from propylene oxide.
  • the polyether polycarbonate polyol is not particularly limited as long as it has structural units derived from an initiator having a specific structure, structural units derived from a cyclic ether having a specific structure, and structural units derived from carbon dioxide. , for example, polyvalent polyether polycarbonate polyols represented by the following general formula (X), etc., and divalent polyether polycarbonate diols represented by the following general formula (I) are preferred.
  • W represents a divalent or trivalent organic group
  • q is 2 or 3
  • R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms
  • m is 0 to 3.0
  • n is 1.0 to 3.0.
  • the plurality of R 2 may be the same or different
  • the plurality of n may be the same number or different numbers
  • a plurality of m may be the same number or different numbers.
  • W represents a divalent organic group, and the number of terminal hydroxyl groups in the general formula (X) is 2.
  • W represents a trivalent organic group, and the number of terminal hydroxyl groups in the general formula (X) is three.
  • the divalent organic group of W includes, for example, a divalent hydrocarbon group having 2 to 12 carbon atoms, a residue of a polyoxyalkylenediol having a molecular weight of 40 to 3000 from which the hydroxyl group at the molecular chain end is removed, and Examples include residues obtained by removing hydroxyl groups from polycarbonate diols having a molecular weight of 300 to 3,000, preferably linear or branched alkylene groups having 4 to 8 carbon atoms, and polyoxyalkylene diols having a molecular weight of 55 to 2,000.
  • Examples of the trivalent organic group for W include (i) a trivalent hydrocarbon group having 2 to 12 carbon atoms; (ii) glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2 , 3-butanetriol, polyoxyalkylenetriol having a molecular weight of 200 to 3,000, and polycarbonate triol having a molecular weight of 300 to 3,000.
  • glycerin trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2,3-butanetriol, polyoxyalkylenetriol having a molecular weight of 210 to 2000 and a residue obtained by removing a hydroxyl group from one selected from the group consisting of polycarbonate triols having a molecular weight of 400 to 2000, more preferably glycerin, trimethylolmethane, trimethylolethane, trimethylolpropane, 1,2, It is a residue obtained by removing a hydroxyl group from one selected from the group consisting of 3-butanetriol, polyoxyalkylenetriol having a molecular weight of 220 to 1,500, and polycarbonate triol having a molecular weight of 450 to 1,500.
  • R 2 is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, more preferably a tetramethylene group, a propylene group or an ethylene group, still more preferably a propylene group or an ethylene group.
  • the n is preferably 1.0 to 3.0, more preferably 1.2 to 2.8, from the viewpoint of good oleic acid resistance.
  • the m is preferably 0 to 3.0, more preferably 1.0 to 3.0, still more preferably 1.2 to 2.8, from the viewpoint of flexibility development and good resistance to oleic acid. is.
  • a structure represented by (-OR 2 -) m may be formed next to W.
  • R 2 in (-OR 2 -) m is different, the structure represented by (-OR 2 -) m may be either a random structure or a block structure. .
  • R 1 is a divalent hydrocarbon group having 2 to 12 carbon atoms, a residue obtained by removing a hydroxyl group at the molecular chain end from a polyoxyalkylenediol having a molecular weight of 40 to 3000, and a molecular weight. represents a residue obtained by removing a hydroxyl group from a polycarbonate diol having 300 to 3000, R 2 represents a divalent hydrocarbon group having 2 to 10 carbon atoms, m is 0 to 3.0, and n is 1.0 to 3.0.
  • a plurality of R 2 may be the same or different, and a plurality of n may be the same number or different numbers. , a plurality of m may be the same number or may be different numbers.
  • R 1 is preferably a linear or branched alkylene group having 4 to 8 carbon atoms, a residue obtained by removing a hydroxyl group at the molecular chain end from a polyoxyalkylene diol having a molecular weight of 55 to 2000, and a molecular weight of 400 to 2000 from which a hydroxyl group is removed, more preferably a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a polyoxyalkylene diol having a molecular weight of 60 to 1500 and a molecular chain terminal residue of It is a residue obtained by removing a hydroxyl group and a residue obtained by removing a hydroxyl group from a polycarbonate diol having a molecular weight of 450 to 1,500.
  • R 2 is preferably a linear or branched alkylene group having 2 to 6 carbon atoms, more preferably a tetramethylene group, a propylene group or an ethylene group, still more preferably a propylene group or an ethylene group.
  • the n is preferably 1.0 to 3.0, more preferably 1.2 to 2.8, from the viewpoint of good oleic acid resistance.
  • the m is preferably 0 to 3.0, more preferably 1.0 to 3.0, still more preferably 1.2 to 2.8, from the viewpoint of flexibility development and good resistance to oleic acid. is.
  • a structure represented by (—OR 2 —) m may be formed at one end or both ends of R 1 .
  • R 2 in (-OR 2 -) m is different, the structure represented by (-OR 2 -) m may be either a random structure or a block structure. .
  • the polyisocyanate compound is not particularly limited as long as it is a compound having a plurality of isocyanate groups in one molecule, but a diisocyanate compound is preferable from the viewpoint of improving the flexibility of the polyurethane resin.
  • Diisocyanate compounds include, for example, 4,4′-diphenylmethane diisocyanate (hereinafter sometimes referred to as “MDI”), naphthalene-1,5-diisocyanate, polyphenylenepolymethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6- Aromatic diisocyanate compounds such as tolylene diisocyanate; aralkyl diisocyanate compounds such as tetramethylxylylene diisocyanate and xylylene diisocyanate; aliphatic diisocyanate compounds such as hexamethylene diisocyanate; Alicyclic diisocyanate compound; urethane modified product obtained from diisocyanate compound; burette modified product obtained from diisocyanate compound; allophanate modified product obtained from diisocyanate compound; carbodiimide modified product obtained from diisocyanate compound; isocyanurate modified product obtained from diisocyanate compound body;
  • aromatic diisocyanate compounds are preferable, 4,4'-diphenylmethane diisocyanate is more preferable, and from the viewpoint of easily suppressing yellowing over time, aliphatic Diisocyanate compounds and alicyclic diisocyanate compounds are preferred, and hexamethylene diisocyanate and isophorone diisocyanate are more preferred.
  • the ratio of the isocyanate groups of the polyisocyanate compound to the hydroxyl groups of the polyether polycarbonate polyol ((the number of isocyanate groups contained in the polyisocyanate compound) / (the number of hydroxyl groups contained in the polyether polycarbonate polyol) ⁇ 100) is the isocyanate group index. Although not particularly limited, it is preferably 150-300, more preferably 180-280.
  • the molecular weight of the polyisocyanate compound is not particularly limited, it is preferably 120-400, more preferably 130-390, and particularly preferably 140-380. When the molecular weight of the polyisocyanate compound is within the above range, the resulting polyurethane resin has better strength.
  • the polyurethane resin of the present invention further contains a structural unit derived from a chain extender.
  • the chain extender is at least one selected from the group consisting of polyols and polyamines, and preferably has at least two active hydrogens that react with isocyanate groups.
  • chain extender examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8 - linear diols such as octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1, 3-propanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2- ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-methyl-1,
  • ethylene glycol, propylene glycol, 1,4-butanediol, 1,6- Hexanediol is preferred, and 1,4-butanediol is more preferred.
  • the molecular weight of the chain extender is not particularly limited, it is preferably 60 to 1,000, more preferably 60 or more and less than 300. When the molecular weight of the chain extender is within the above range, the flexibility and strength of the resulting polyurethane resin can be further improved.
  • the proportion of each structural unit in the polyurethane resin can be obtained, for example, as follows.
  • a polyurethane resin is placed in a polytetrafluoroethylene-coated pressure vessel together with pyridine and distilled water and heated at 130° C. for 15 hours. Thereafter, pyridine is distilled off to obtain a solution dissolved in tetrahydrofuran.
  • measurement is performed by preparative GPC (eg, LC-Force, product name of YMC), and a portion of the measurement solution corresponding to each peak is collected for the obtained peaks.
  • Tetrahydrofuran is removed from each of the measured solutions corresponding to the separated peaks by drying under reduced pressure at 80° C.
  • the number average molecular weight (Mn) of the polyurethane resin is not particularly limited, but is preferably over 800, more preferably 1,000 to 120,000, still more preferably 2,000 to 100,000, and particularly preferably 5,000. 000 to 60,000. When the number average molecular weight (Mn) of the polyurethane resin is more than 800, the flexibility is better, and when it is 120,000 or less, the flexibility and strength are better.
  • the number average molecular weight of the polyurethane resin is measured by the method described in Examples below.
  • the transparency (haze) of the polyurethane resin is not particularly limited, but is preferably less than 30, more preferably 28 or less, still more preferably 27 or less.
  • the transparency (haze) of the polyurethane resin is measured by the method described in Examples below.
  • the stress (M100) of the polyurethane resin is not particularly limited, but is preferably 1.5 MPa or more, more preferably 1.5 to 5.0 MPa, still more preferably 1.8 to 4.0 MPa.
  • the breaking strength (Tmax) of the polyurethane resin is not particularly limited, but is preferably 13 MPa or more, more preferably 13 to 60 MPa, and still more preferably 14 to 50 MPa.
  • the breaking elongation (L) of the polyurethane resin is not particularly limited, but is preferably 400% or more, more preferably 400 to 1000%, and still more preferably 500 to 900%.
  • the storage modulus E' (25°C) of the polyurethane resin is not particularly limited, but is preferably 0.01 MPa or more, more preferably 0.1 to 100 MPa, and still more preferably 0.3 to 15 MPa.
  • the hydrolysis resistance of the polyurethane resin is not particularly limited, but is preferably 80.0 to 100.0%, more preferably 85.0 to 100.0%, still more preferably 90.0 to 100.0%. is.
  • the oleic acid resistance of the polyurethane resin is not particularly limited, but is preferably 0.5 to 15.0%, more preferably 1.0 to 10.0%, still more preferably 1.0 to 5.0%. be.
  • Method for producing polyurethane resin In the method for producing a polyurethane resin of the present invention, an initiator having an active hydrogen-containing group and having 3.0 or less structural units derived from a cyclic ether per molecule, a cyclic ether, and carbon dioxide, A method for producing a polyurethane resin by polymerizing in the presence of a catalyst to obtain a polyether polycarbonate polyol and reacting the polyether polycarbonate polyol with a polyisocyanate compound, In the polyether polycarbonate polyol, the average chain number of structural units derived from cyclic ether is 1.0 or more and 3.0 or less.
  • an initiator having an active hydrogen-containing group and having 3.0 or less structural units derived from a cyclic ether per molecule, a cyclic ether, and carbon dioxide are combined.
  • a catalyst to obtain a polyether polycarbonate polyol.
  • the initiator and the cyclic ether those described in the section [Polyurethane resin] can be used.
  • the ring-opening addition polymerization when two or more cyclic ethers are reacted with an initiator and carbon dioxide may be random polymerization or block polymerization, or a combination of random polymerization and block polymerization. may be
  • the catalyst is not particularly limited, and examples thereof include double metal cyanide complex catalysts such as TBA-based double metal cyanide complex catalysts (hereinafter sometimes referred to as "DMC catalysts"); metal-salen complex catalysts such as cobalt-salen catalysts.
  • DMC catalysts double metal cyanide complex catalysts
  • metal-salen complex catalysts such as cobalt-salen catalysts.
  • alkali catalysts such as sodium hydroxide, potassium hydroxide, and cesium hydroxide
  • Ziegranatta catalysts composed of organoaluminum compounds and transition metal compounds
  • metal-coordinated porphyrin catalysts as complexes obtained by reacting porphyrins
  • phosphazene catalysts containing phosphazenium salts
  • tris(pentafluorophenyl)borane reduced Robson's type macrocyclic ligand catalysts (catalysts composed of reduced Robson's type macrocyclic ligands); These may be used individually by 1 type, and may be used 2 or more types.
  • the DMC catalyst is not particularly limited, and examples thereof include a zinc hexacyanocobaltate complex whose ligand is t-butyl alcohol (hereinafter sometimes referred to as "TBA-DMC catalyst"), and a ligand of ethylene glycol dimethyl ether (" and a zinc hexacyanocobaltate complex whose ligand is diethylene glycol dimethyl ether (sometimes referred to as "diglyme”). These may be used individually by 1 type, and may be used 2 or more types. Among these catalysts, the TBA-DMC catalyst is preferable from the viewpoint that the activity during polymerization is higher and the Mw/Mn of the polyether polycarbonate polyol can be made narrower, resulting in a lower viscosity.
  • the metal-salen complex catalyst is not particularly limited. are mentioned. These may be used individually by 1 type, and may be used 2 or more types.
  • the catalyst preferably contains at least one selected from the group consisting of a DMC catalyst and a metal-salen complex catalyst, from the viewpoint of easily adjusting the introduction rate of carbon dioxide in the polyether polycarbonate diol to the preferred range of the present application.
  • the catalyst is a polyether polycarbonate polyol of a perfect alternating polymer (for example, a compound represented by the following general formula (II) (R 1 and n: same as general formula (I), CO 2 content: 50 mol% degree)), metal-coordinated porphyrin catalysts and metal-salen complex catalysts are preferred.
  • the catalyst is a random polymer polyether polycarbonate polyol (for example, a compound represented by the following general formula (III) (R 1 , m, and n: the same as in general formula (I), CO 2 content: From the viewpoint of obtaining several mol % to 30 mol %)), metal-salen complex catalysts, DMC catalysts, and reduced Robson-type macrocyclic ligand catalysts are preferable, and DMC catalysts are more preferable.
  • general formula (III) R 1 , m, and n: the same as in general formula (I), CO 2 content: From the viewpoint of obtaining several mol % to 30 mol %)
  • metal-salen complex catalysts, DMC catalysts, and reduced Robson-type macrocyclic ligand catalysts are preferable, and DMC catalysts are more preferable.
  • the amount of the catalyst added is not particularly limited as long as it is an amount necessary for the polymerization of carbon dioxide and the ring-opening polymerization of the cyclic ether, but it is preferably as small as possible, and 100 parts by mass of the obtained polyether polycarbonate polyol. , preferably 0.001 to 10 parts by mass, more preferably 0.002 to 5 parts by mass, and particularly preferably 0.05 to 3 parts by mass.
  • the smaller the amount of the catalyst added the smaller the amount of catalyst contained in the resulting polyether polycarbonate polyol. Thereby, the influence of the catalyst on the reactivity between the polyether polycarbonate polyol and the polyisocyanate compound can be reduced, and the cost can be reduced.
  • the polymerization reaction is preferably carried out under a pressure of 0.1 to 15 MPa, more preferably under a pressure of 0.2 to 10 MPa, and carried out under a pressure of 0.3 to 8 MPa. is particularly preferred.
  • the polymerization temperature for the polymerization reaction is not particularly limited, but is preferably 30 to 180°C, more preferably 70 to 160°C, and particularly preferably 80 to 140°C.
  • the polymerization temperature is 30° C. or higher, the polymerization of carbon dioxide and the ring-opening polymerization of the cyclic ether can be reliably started, and when it is 180° C. or lower, the deterioration of the polymerization activity of the catalyst can be suppressed.
  • the polymerization time for the polymerization reaction is not particularly limited, but is preferably 2 to 18 hours, more preferably 2 to 14 hours, particularly preferably 2 to 10 hours.
  • the reaction performance is excellent, and when it is 18 hours or less, the economy is excellent.
  • the amount of the cyclic ether charged is not particularly limited, but is preferably 3.0 to 99.0 parts by mass, more preferably 4.0 to 98.0 parts by mass, per 100 parts by mass of the obtained polyether polycarbonate polyol. 0 parts by weight, particularly preferably 5.0 to 97.0 parts by weight.
  • the amount of the cyclic ether to be charged is within the above range, good flexibility can be exhibited when the urethane resin is formed.
  • the amount of carbon dioxide charged is not particularly limited, but is preferably 0.05 to 40 parts by mass, more preferably 0.10 to 35 parts by mass, based on 100 parts by mass of the polyether polycarbonate polyol obtained. Particularly preferably, it is 1.15 to 30 parts by mass.
  • the amount of carbon dioxide charged is within the above range, the urethane resin can exhibit good strength and resistance to oleic acid.
  • a polyurethane resin is obtained by reacting the obtained polyether polycarbonate polyol with a polyisocyanate compound.
  • a polyisocyanate compound those described in the [Polyurethane Resin] section can be used.
  • the polyurethane resin of the present invention can be obtained by reacting the polyether polycarbonate polyol with the polyisocyanate compound to obtain an NCO-terminated prepolymer, and then reacting the prepolymer with a chain extender. . Moreover, after reacting the prepolymer with the chain extender, the prepolymer may be further reacted with a polyisocyanate compound. Alternatively, the polyether polycarbonate polyol may be reacted with the polyisocyanate compound to obtain an NCO-terminated prepolymer, and then the prepolymer may be reacted with a polyfunctional alcohol.
  • a polyol may be reacted with the polyisocyanate compound to obtain a hydroxyl-terminated prepolymer, and then the prepolymer and the polyisocyanate compound may be reacted.
  • the chain extender those described in the section [Polyurethane resin] can be used.
  • the polyfunctional alcohol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol.
  • glycerin trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, 1,2,6-hexanetriol, diglycerin, dipentaerythritol, polyoxyalkylene glycol having a hydroxyl value equivalent molecular weight of 6000 or less, polyoxyalkylene triol mentioned.
  • the ratio of the total mass of the polyisocyanate compound and the chain extender to the total mass of the polyisocyanate compound, the chain extender, and the polyether polycarbonate polyol (hereinafter referred to as "hard segment content”) is preferably 10 to 40% by mass, more preferably 15 to 30% by mass.
  • hard segment content is measured by the method described in Examples below.
  • the mass of the polyisocyanate compound relative to the total mass of the polyisocyanate compound, the chain extender, and the polyether polycarbonate polyol (hereinafter referred to as "NCO unit content") is preferably 10 to 40% by mass, more preferably 15 to 30% by mass.
  • NCO unit content of the polyurethane resin is 10% by mass or more, the flexibility becomes better, and when it is 40% by mass or less, the flexibility and strength become better.
  • the NCO unit content of the polyurethane resin is measured by the method described in Examples below.
  • a reaction catalyst may be used when reacting the polyether polycarbonate polyol and the polyisocyanate compound.
  • the reaction catalyst is not particularly limited, and examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and 2-ethylhexanoic acid.
  • Organic tin compounds such as tin; iron compounds such as iron acetylacetonate and ferric chloride; tertiary amine catalysts such as triethylamine and triethylenediamine; and other known urethanization reaction catalysts.
  • the amount of the reaction catalyst to be added is not particularly limited, but is preferably 0.00 to 100 parts by mass of the polyether polycarbonate polyol. 001 to 5 parts by mass, more preferably 0.005 to 0.1 parts by mass, particularly preferably 0.01 to 0.05 parts by mass.
  • the amount of the reaction catalyst added is 0.001 parts by mass or more, the reactivity is more excellent, and when it is 5 parts by mass or less, impurities derived from the catalyst can be further reduced.
  • the temperature at which the polyether polycarbonate polyol and the polyisocyanate compound are reacted is not particularly limited, but is preferably 15 to 160°C, more preferably 30 to 150°C, and particularly preferably 50 to 140°C.
  • the temperature at which the polyether polycarbonate polyol and the polyisocyanate compound are reacted is 15° C. or higher, the reaction can be reliably started, and when it is 160° C. or lower, the reaction can be easily controlled.
  • the reaction time for reacting the polyether polycarbonate polyol and the polyisocyanate compound is not particularly limited, but is preferably 0.5 to 100 hours, more preferably 1 to 10 hours, and particularly preferably 2 to 6 hours. be. When the reaction time is 0.5 hours or more, the reaction performance is more excellent, and when it is 100 hours or less, the economy is more excellent.
  • a solvent may be used when the polyether polycarbonate polyol and the polyisocyanate compound are reacted.
  • the solvent is not particularly limited, and examples thereof include ethers such as tetrahydrofuran and dioxane; amides such as dimethylformamide and dimethylacetamide; sulfoxides such as dimethylsulfoxide; ketones such as acetone, methyl ethyl ketone and cyclohexanone; esters such as butyl; secondary alcohols such as isopropyl alcohol; aromatic hydrocarbons such as toluene and xylene; These may be used individually by 1 type, and may be used 2 or more types.
  • the polyurethane resin of the present invention can be suitably used in a wide range of fields such as adhesives, pressure-sensitive adhesives, paints, coating agents, synthetic leathers, artificial leathers, elastomers, elastic fibers, floor materials, printing ink binders and the like.
  • As standard samples for molecular weight measurement several types of monodisperse polystyrene with different degrees of polymerization were measured using a commercially available GPC measurement device (HLC-8320GPC, manufactured by Tosoh Corporation), and the relationship between the molecular weight of polystyrene and the retention time was determined.
  • the area S1 of the 3H peak (1.34 ppm) derived from the methyl group of propylene oxide PO as a cyclic ether flanked by carbonate on both ends, one for CO2 and the other for the methyl group of PO flanked by PO Based on the area S2 of the derived 3H peak (1.29 ppm) and the area S3 of the methyl group derived 3H peak (1.14 ppm) of PO adjacent to both ends, CO 2 -PO- The ratio of CO 2 chains (percentage of perfect alternating copolymer), the ratio of PO—PO—CO 2 chains (percentage of random copolymer), and the ratio of PO—PO—PO chains (percentage of PPG) were calculated.
  • the formula weight of PO having both ends adjacent to carbonate is 102
  • the formula weight of PO having one end adjacent to carbonate and the other end adjacent to PO is 102
  • the formula weight of PO having both ends adjacent to PO is 58. bottom.
  • (Ratio of CO 2 -PO-CO 2 chains [% by mass]) S1 x 102/(S1 x 102 + S2 x 102 + S3 x 58) x 100
  • Proportion of PO-PO-CO 2 chains [% by mass]) S2 ⁇ 102 / (S1 ⁇ 102 + S2 ⁇ 102 + S3 ⁇ 58) ⁇ 100
  • Percentage of PO-PO-PO chains [mass%]) S3 x 58/(S1 x 102 + S2 x 102 + S3 x 58) x 100
  • the ratio of structural units derived from carbon dioxide in the polyether polycarbonate polyol (CO 2 (formula weight 44) ratio) is obtained, and the molecule of the structural unit derived from carbon dioxide in the polyether polycarbonate polyol calculated the number.
  • CO2 ratio [mass%]) (S1 + S2) / ⁇ (S1 x 102 + S2 x 102 + S3 x 58) ⁇ x 44 x 100
  • Numberer of molecules of structural units derived from carbon dioxide in polyether polycarbonate polyol (hydroxyl value equivalent molecular weight) x (CO 2 ratio) / (44 x 100)
  • the hard segment content shown in Table 2 is the formula of "(mass of polyisocyanate compound + mass of chain extender) / (mass of polyisocyanate compound + mass of chain extender + mass of polyether polycarbonate polyol) x 100". is a value (% by mass) obtained by calculation using
  • NCO unit content The NCO unit content shown in Table 2 was calculated using the formula "(mass of polyisocyanate compound) / (mass of polyisocyanate compound + mass of chain extender + mass of polyether polycarbonate polyol) x 100". It is a value (% by mass) obtained by
  • ⁇ Tensile test> A test piece was obtained by punching out a polyurethane resin film obtained in each example described later with a dumbbell frame (dumbbell No. 3). The resulting test piece was subjected to a tensile test using a tensile tester (product name: Tensilon VTM, manufactured by Toyo Baldwin Co., Ltd.) at a tensile speed of 300 mm / min, and according to the test method of JIS K6251 (2017). , stress at 100% elongation (M100, unit: MPa), breaking strength (Tmax, unit: MPa), and breaking elongation (L, unit: %) were measured. Table 2 shows the measurement results.
  • the stress (M100) is in the range of 1.5 MPa or more, it can be said that the mechanical strength of the film is good.
  • breaking strength (Tmax) is in the range of 13 MPa or more, it can be said that the toughness of the film is good.
  • elongation at break (L) is in the range of 400% or more, it can be said that the flexibility of the film is good.
  • ⁇ Storage modulus> A polyurethane resin film obtained in each example described later was cut into a size of 5 mm ⁇ 10 mm and used as a test sample.
  • the storage modulus E' (MPa) at 25°C of the obtained test sample was measured under the following conditions. Table 2 shows the measurement results.
  • ⁇ Transparency (Haze)> A polyurethane resin film obtained in each example described later was cut into a size of 40 mm ⁇ 40 mm to prepare a test sample. The haze of the resulting test sample was measured using a simultaneous color/turbidity measuring instrument (product name: COH400, manufactured by Nippon Denshoku Industries Co., Ltd.). Table 2 shows the measurement results. Transparency is good when the haze value is less than 30, and poor when it is 30 or more.
  • ⁇ Oleic acid resistance> A polyurethane resin film obtained in each example described later was cut into a size of about 30 mm ⁇ 30 mm to prepare a test sample. The resulting test sample was immersed in oleic acid at 23° C. for one week, then taken out and weighed. The mass change rate (%) compared with the mass before the oleic acid resistance test was calculated. Table 2 shows the results. If the mass change rate is 15% or less, the oleic acid resistance is good.
  • the reactant was removed from the reaction vessel, and the hydroxyl value was 61.0 mg-KOH/g, Mn was 2200, Mw/Mn was 1.65, the CO 2 ratio was 20.0% by mass, and the PO-PO average chain number was 406 g of 2.5 polyether polycarbonate polyol (a2) were obtained.
  • the amount of carbon dioxide added during the reaction was 88 g and the yield was 92%.
  • reaction product was taken out from the reaction vessel to obtain 299 g of a polyether polycarbonate polyol precursor (a4') having a hydroxyl value of 124.7 mg-KOH/g and a CO 2 ratio of 38.1% by mass.
  • the amount of carbon dioxide added during the reaction was 127 g and the yield was 90%.
  • To the reactor was added 151 g of polyether polycarbonate polyol precursor (a4') and 0.05 g of TBA-DMC catalyst.
  • reaction vessel is heated to 130 ° C., carbon dioxide is introduced, pressurized (about 2.0 MPa), and then depressurized (about 0.1 MPa). After repeating a series of operations three times, at the time of catalyst activation of carbon dioxide pressure was increased to 0.5 MPa. Next, 11 g of propylene oxide (PO) was added, and after confirming heat generation, the liquid temperature was lowered to 90° C., the carbon dioxide pressure during synthesis was maintained at 0.5 MPa, and 95 g of PO was added over 12 hours. After reacting at 90° C. for 3 hours, the liquid temperature was raised to 130° C. and held under reduced pressure for 5 hours to remove propion carbonate as a by-product.
  • PO propylene oxide
  • the reactant was removed from the reaction vessel, and the hydroxyl value was 57.8 mg-KOH/g, Mn was 2030, Mw/Mn was 1.60, the CO 2 ratio was 21.0% by mass, and the PO-PO average chain number was 315 g of 2.6 polyether polycarbonate polyol (a4) were obtained.
  • the amount of carbon dioxide added during the reaction was 11 g and the yield was 97%.
  • the liquid temperature was raised to 130° C. and held under reduced pressure for 5 hours to remove propion carbonate as a by-product.
  • the reactant was removed from the reaction vessel, and the hydroxyl value was 59.1 mg-KOH/g, Mn was 2250, Mw/Mn was 1.20, the CO 2 ratio was 8.0% by mass, and the PO-PO average chain number was 290 g of polyether polycarbonate polyol (c1) of 6.2 was obtained.
  • the amount of carbon dioxide added during the reaction was 24 g and the yield was 95%.
  • Example 1 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (a1), 77.0 g of 4,4′-diphenylmethane diisocyanate (hereinafter sometimes referred to as “MDI”) (isocyanate group index: 217), and an antioxidant ( 3.4 g of Irganox 1010 (manufactured by BASF) was mixed, heated to 80° C. and reacted for 4.0 hours to obtain an isocyanate group-terminated precursor.
  • MDI 4,4′-diphenylmethane diisocyanate
  • the obtained isocyanate group-terminated precursor and 15.5 g of 1,4-butanediol (1,4-BD) as a chain extender were mixed, and the resulting mixture was transferred to a stainless steel palette and further heated to 130 ° C. for 4.0 hours to obtain a polyurethane resin (A1) having a hard segment content of 25%. Also, the obtained polyurethane resin (A1) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 2 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (a2), 73.2 g of MDI (isocyanate group index: 215), and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80°C. After reacting for 4.0 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 14.6 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (A2) having a hard segment content of 25%. The obtained polyurethane resin (A2) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 3 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (a3), 73.0 g of MDI (isocyanate group index: 218), and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80°C. After reacting for 3.5 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 14.8 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (A3) having a hard segment content of 25%. Also, the obtained polyurethane resin (A3) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 4 In a reaction vessel, 250 g of polyether polycarbonate polyol (a4), 71.1 g of MDI (isocyanate group index: 220) and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80° C. to give 4. After reacting for 0 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 14.5 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (A4) having a hard segment content of 25%. Also, the obtained polyurethane resin (A4) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 5 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (c1), 71.2 g of MDI (isocyanate group index: 216), and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80°C. After reacting for 4.0 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 14.3 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (C1) having a hard segment content of 25%. Also, the obtained polyurethane resin (C1) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 6 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (c2), 71.2 g of MDI (isocyanate group index: 218), and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80°C. After reacting for 4.5 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 14.4 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (C2) having a hard segment content of 25%. Also, the obtained polyurethane resin (C2) was molded at a temperature of 200° C. using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 7 In a reaction vessel, 250.0 g of polyether polycarbonate polyol (c3), 76.8 g of MDI (isocyanate group index: 220), and 3.4 g of the same antioxidant as in Example 1 are mixed and heated to 80°C. After reacting for 6.0 hours, an isocyanate group-terminated precursor was obtained. Next, the obtained isocyanate group-terminated precursor and 15.6 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , a polyurethane resin (C3) having a hard segment content of 25% was obtained. Also, the obtained polyurethane resin (C3) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 8 In a reaction vessel, 250.0 g of polycarbonate diol (product name: T6002, manufactured by Asahi Kasei Corporation, Mn: 2,100), 69.0 g of MDI (isocyanate group index: 220), and the same antioxidant as in Example 13. 3 g were mixed, heated to 80° C. and reacted for 3.0 hours to obtain an isocyanate group-terminated precursor. Next, the obtained isocyanate group-terminated precursor and 14.1 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours. , to obtain a polyurethane resin (C4) having a hard segment content of 25%. Also, the obtained polyurethane resin (C4) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • polycarbonate diol product name: T6002, manufactured by Asahi Kasei Corporation, Mn: 2,100
  • Example 9 150.0 g of polycarbonate diol (product name: T6002, manufactured by Asahi Kasei Corporation, Mn: 2,100) and 100.0 g of polyester polyol (product name: Teslac 2426, manufactured by Showa Denko Corporation, Mn: 1,000) were placed in a reaction vessel. , MDI 69.1 g (isocyanate group index: 223), and 3.3 g of the same antioxidant as in Example 1 were mixed, heated to 80 ° C. and reacted for 3.0 hours to obtain an isocyanate group-terminated precursor. .
  • polycarbonate diol product name: T6002, manufactured by Asahi Kasei Corporation, Mn: 2,100
  • polyester polyol product name: Teslac 2426, manufactured by Showa Denko Corporation, Mn: 1,000
  • the obtained isocyanate group-terminated precursor and 14.2 g of 1,4-BD as a chain extender are mixed, and the obtained mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours.
  • a polyurethane resin (C5) having a hard segment content of 25% was obtained.
  • the obtained polyurethane resin (C5) was molded using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • Example 10 In a reaction vessel, 250.0 g of polypropylene glycol (PPG) (product name: EL2020, manufactured by AGC, Mn: 2,010), 69.0 g of MDI (isocyanate group index: 225), and the same antioxidant as in Example 1 3.3 g of the agent was mixed, heated to 80° C. and reacted for 6.5 hours to obtain an isocyanate group-terminated precursor. Next, the resulting isocyanate group-terminated precursor and 14.3 g of 1,4-BD as a chain extender are mixed, and the resulting mixture is transferred to a stainless steel palette and further reacted at 130 ° C. for 4.0 hours.
  • PPG polypropylene glycol
  • MDI isocyanate group index: 225
  • the obtained polyurethane resin (C6) was molded at a temperature of 200° C. using a hydraulic molding machine to obtain a film having a thickness of about 250 ⁇ m.
  • the hard segment content (% by mass), NCO unit content (% by mass), and number average molecular weight (Mn) of the obtained polyurethane resin and the tensile properties (stress M100 ( MPa), breaking strength Tmax (MPa), breaking elongation L (%)), storage elastic modulus E′ (MPa), transparency, hydrolysis resistance (%), and oleic acid resistance (%) were measured or evaluated.
  • the measurement results and evaluation results are shown in Table 2.
  • the polyurethane resins of Examples 1 to 4 gave good results in terms of tensile properties, storage modulus E' resistance to hydrolysis, and resistance to oleic acid. It can be seen that it is superior to Further, the polyurethane resins of Examples 1 to 4 all have a haze value of less than 30 and are excellent in transparency.
  • the polyurethane resin obtained by the present invention can be suitably used in a wide range of fields such as adhesives, adhesives, paints, coating agents, synthetic leathers, artificial leathers, elastomers, elastic fibers, flooring materials, printing ink binders, and the like.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention concerne une résine de polyuréthane possédant un motif structural dérivé d'un polyol de polycarbonate de polyéther et un motif structural dérivé d'un composé polyisocyanate, le polyol de polycarbonate de polyéther possédant un motif structural dérivé d'un initiateur, un motif structural dérivé d'un éther cyclique et un motif structural dérivé du dioxyde de carbone ; l'initiateur possédant un groupe contenant de l'hydrogène actif ; 3,0 ou moins de motifs structuraux dérivés d'un éther cyclique étant présents par molécule ; et le polyol de polycarbonate de polyéther possédant un nombre de chaînes moyen de motifs structuraux dérivés d'un éther cyclique de 1,0 à 3,0 inclus.
PCT/JP2022/029044 2021-08-06 2022-07-28 Résine de polyuréthane et son procédé de production WO2023013510A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2023540295A JPWO2023013510A1 (fr) 2021-08-06 2022-07-28

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021130235 2021-08-06
JP2021-130235 2021-08-06

Publications (1)

Publication Number Publication Date
WO2023013510A1 true WO2023013510A1 (fr) 2023-02-09

Family

ID=85154465

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/029044 WO2023013510A1 (fr) 2021-08-06 2022-07-28 Résine de polyuréthane et son procédé de production

Country Status (2)

Country Link
JP (1) JPWO2023013510A1 (fr)
WO (1) WO2023013510A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023204068A1 (fr) * 2022-04-22 2023-10-26 Ａｇｃ株式会社 Composition d'adhésif, objet durci de cette composition d'adhésif, et procédé de fabrication de cette composition d'adhésif

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010509479A (ja) * 2006-11-15 2010-03-25 ビーエーエスエフ ソシエタス・ヨーロピア 柔軟なポリウレタンフォームを製造する方法
JP2014524965A (ja) * 2011-07-25 2014-09-25 ノボマー， インコーポレイテッド ポリウレタンに使用するための脂肪族ポリカーボネート
JP2015533915A (ja) * 2012-11-09 2015-11-26 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ ポリエーテルカーボナートポリオールの製造方法
JP2016527385A (ja) * 2013-08-12 2016-09-08 レプソル・ソシエダッド・アノニマＲｅｐｓｏｌ．Ｓ．Ａ． ポリエーテルカーボネートポリオールの製造方法
JP2018536065A (ja) * 2015-11-19 2018-12-06 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ポリエーテルカーボネートポリオール系ポリウレタンフォーム
JP2019525804A (ja) * 2016-07-15 2019-09-12 コベストロ・エルエルシー ポリエーテルカーボネートポリオールより調製したカーペットおよび人工芝基布
JP2020535254A (ja) * 2017-09-25 2020-12-03 エボニック オペレーションズ ゲーエムベーハー ポリウレタンフォームの製造
JP2021038278A (ja) * 2019-08-30 2021-03-11 三菱ケミカル株式会社 合成皮革用ポリウレタン

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010509479A (ja) * 2006-11-15 2010-03-25 ビーエーエスエフ ソシエタス・ヨーロピア 柔軟なポリウレタンフォームを製造する方法
JP2014524965A (ja) * 2011-07-25 2014-09-25 ノボマー， インコーポレイテッド ポリウレタンに使用するための脂肪族ポリカーボネート
JP2015533915A (ja) * 2012-11-09 2015-11-26 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ ポリエーテルカーボナートポリオールの製造方法
JP2016527385A (ja) * 2013-08-12 2016-09-08 レプソル・ソシエダッド・アノニマＲｅｐｓｏｌ．Ｓ．Ａ． ポリエーテルカーボネートポリオールの製造方法
JP2018536065A (ja) * 2015-11-19 2018-12-06 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ ポリエーテルカーボネートポリオール系ポリウレタンフォーム
JP2019525804A (ja) * 2016-07-15 2019-09-12 コベストロ・エルエルシー ポリエーテルカーボネートポリオールより調製したカーペットおよび人工芝基布
JP2020535254A (ja) * 2017-09-25 2020-12-03 エボニック オペレーションズ ゲーエムベーハー ポリウレタンフォームの製造
JP2021038278A (ja) * 2019-08-30 2021-03-11 三菱ケミカル株式会社 合成皮革用ポリウレタン

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023204068A1 (fr) * 2022-04-22 2023-10-26 Ａｇｃ株式会社 Composition d'adhésif, objet durci de cette composition d'adhésif, et procédé de fabrication de cette composition d'adhésif

Also Published As

Publication number Publication date
JPWO2023013510A1 (fr) 2023-02-09

Similar Documents

Publication Publication Date Title
CN101535364B (zh) 生产软质聚氨酯泡沫的方法
CN104837885B (zh) 基于聚醚碳酸酯多元醇的新型热塑性聚氨酯弹性体的制造和用途
JP3097854B2 (ja) ポリウレタン類の製造方法
EP2566906B1 (fr) Prépolymères de polyisocyanate et leur utilisation
JPWO2005116102A1 (ja) ポリウレタンエラストマーおよびその製造方法
KR20100125239A (ko) 하이드록시 화합물, 그 제조 방법, 그 하이드록시 화합물을 사용한 프리폴리머 및 폴리우레탄
JP5827745B2 (ja) ポリウレタン
JP2017048305A (ja) 熱硬化型ポリウレタン
JP2017511414A (ja) 熱可塑性ポリウレタン、その製造方法および使用
JP5169752B2 (ja) 軟質ポリウレタンフォームの製造方法
WO2023013510A1 (fr) Résine de polyuréthane et son procédé de production
US20180037693A1 (en) Polybutadienols for producing glassy polyurethanes
EP3753967A1 (fr) Polyétherpolyol, et liquide de système polyol
JP6341405B2 (ja) ウレタン組成物及びウレタンエラストマー成形品
JP2023103299A (ja) ポリカーボネートジオール組成物
JPH04164914A (ja) 靴底用二液性気泡質ポリウレタンエラストマー組成物
JP2002030129A (ja) 微発泡ポリウレタンエラストマー及びその製造方法
US6723836B1 (en) Low odor polyoxyalkylene polyol, process for producing the same and urethane composition
JP5650839B2 (ja) 合成皮革用ポリウレタン樹脂に用いられる強伸度向上剤並びにこれを用いたポリオール組成物及びポリウレタン樹脂
JP7296807B2 (ja) ポリウレタン
JP4962085B2 (ja) ポリオキサレートポリオールおよびそれから誘導されるポリオキサレートウレタン
JP7312860B2 (ja) アンヒドロヘキシトールのエーテルジオール由来のポリカーボネートジオール及びその製造方法、並びにそれから製造されたポリウレタン及びそれを含む接着剤
EP3950775B1 (fr) Composition de polyalkylène éther glycol et procédé de production de polyuréthane l'utilisant
JP2003082057A (ja) 熱可塑性ポリウレタンエラストマー、可塑性ポリウレタンエラストマー用組成物、その製造方法
WO2022224996A1 (fr) Composition de polycarbonate diol

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22852933

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023540295

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE