WO2022080491A1 - ポリカーボネートポリオール及びその製造方法、組成物及びその製造方法、ウレタン樹脂、並びに、水性ウレタン樹脂分散体 - Google Patents

ポリカーボネートポリオール及びその製造方法、組成物及びその製造方法、ウレタン樹脂、並びに、水性ウレタン樹脂分散体 Download PDF

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WO2022080491A1
WO2022080491A1 PCT/JP2021/038305 JP2021038305W WO2022080491A1 WO 2022080491 A1 WO2022080491 A1 WO 2022080491A1 JP 2021038305 W JP2021038305 W JP 2021038305W WO 2022080491 A1 WO2022080491 A1 WO 2022080491A1
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composition
formula
group
represented
urethane resin
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PCT/JP2021/038305
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English (en)
French (fr)
Japanese (ja)
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康平 本田
真治 重安
高廣 田中
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Tosoh Corp
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Tosoh Corp
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Priority to EP21880226.2A priority Critical patent/EP4212337A4/en
Priority to JP2022507830A priority patent/JP7081730B1/ja
Priority to KR1020237011931A priority patent/KR102630504B1/ko
Priority to US18/031,232 priority patent/US12065542B2/en
Priority to CN202180069258.5A priority patent/CN116348298B/zh
Priority to JP2022019783A priority patent/JP7088429B2/ja
Priority to TW111110514A priority patent/TWI836382B/zh
Publication of WO2022080491A1 publication Critical patent/WO2022080491A1/ja
Priority to JP2022080680A priority patent/JP2022103293A/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • 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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C08G18/6517—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • 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
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C08G64/305—General preparatory processes using carbonates and alcohols
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/146—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 characterised by the macromolecular diols used

Definitions

  • the present invention relates to a polycarbonate polyol and a method for producing the same, a composition and the method for producing the same, a urethane resin, and an aqueous urethane resin dispersion.
  • polycarbonate polyols are useful as raw materials for producing urethane resins (also called polyurethane resins) by reacting with polyisocyanate compounds, and are useful as raw materials for adhesives, paints, etc. be.
  • the urethane resin obtained from the polyester polyol has a drawback that it is inferior in hydrolysis resistance. Further, since the polyether polyol has an ether bond, the urethane resin obtained from the polyether polyol has a drawback that it is inferior in weather resistance and heat resistance. On the other hand, the urethane resin obtained from the polycarbonate polyol tends to be excellent in durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).
  • Polycarbonate polyol is usually produced by reacting a carbonic acid ester and a diol in the presence of a transesterification catalyst (transesterification reaction).
  • Patent Documents 1 and 2 propose a polycarbonate polyol obtained by a transesterification reaction between a polycarbonate diol and a triol compound and / or a tetraol compound.
  • An object of the present invention is to provide a novel polycarbonate polyol and a method for producing the same, which are useful as raw materials for urethane resins and the like, and urethane resins using the polycarbonate polyol as a raw material.
  • An object of the present invention is also to provide a composition containing the polycarbonate polyol, a method for producing the same, and a urethane resin using the composition as a raw material. It is also an object of the present invention to provide a composition which has good tensile strength, elongation and texture and contributes to the formation of a urethane resin having excellent durability.
  • the present invention provides the following [1] to [23].
  • R 1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 represents an alkanediyl group
  • n and m each represent an integer of 1 or more.
  • a plurality of R 2s may be the same or different from each other.
  • R 1 has the same meaning as described above.
  • the total number of moles of the groups represented by the following formula (a-1) contained in the composition is defined as CA1
  • the total number of moles of the groups represented by the following formula (I) contained in the composition is defined as CA1.
  • R 1 is synonymous with the above, and * indicates a bond. ]
  • the carbonic acid is heated by heating a mixed solution containing a polyhydric alcohol represented by the following formula (B), a diol represented by the following formula (D), a carbonic acid ester, and a transesterification catalyst.
  • a method for producing a polycarbonate polyol wherein a reflux reaction is carried out while removing an alcohol derived from an ester from the reaction system to obtain the polycarbonate polyol according to any one of [1] to [4].
  • R 1 has the same meaning as described above.
  • R 2 has the same meaning as described above.
  • the carbonic acid is heated by heating a mixed solution containing a polyhydric alcohol represented by the following formula (B), a diol represented by the following formula (D), a carbonic acid ester, and a transesterification catalyst.
  • a method for producing a composition wherein a reflux reaction is carried out while removing the alcohol derived from the ester from the reaction system to obtain the composition according to any one of [5] to [10].
  • R 1 has the same meaning as described above.
  • R 2 has the same meaning as described above.
  • the heating of the mixed solution includes heating at a temperature T1 under a pressure of 101.325 kPa ⁇ 20.000 kPa and then heating at a temperature T2 under a reduced pressure of 10.000 kPa or less.
  • the temperatures T1 and T2 satisfy the relationship of the following formulas ( ⁇ ) and ( ⁇ ), and in the reflux reaction, the alcohol derived from the carbonic acid ester is distilled off at 120 ° C. or lower and removed from the reaction system [11]. Or the production method according to [12]. 120 ° C ⁇ T1 ⁇ 155 ° C ... ( ⁇ ) 140 ° C ⁇ T2 ⁇ 155 ° C ... ( ⁇ )
  • the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 with respect to 100 parts by mass of the total amount of the polyhydric alcohol, the diol and the carbonic acid ester in the mixed solution.
  • a urethane resin which is a polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof, and the polyol component contains the polycarbonate polyol according to any one of [1] to [4].
  • CA1 be the total number of moles of the group represented by the following formula (a-1) contained in the polyol component
  • C B be the total number of moles of the polyhydric alcohol contained in the polyol component.
  • the urethane resin according to [17] which has a molar ratio ( CA1 / CB ) of 0.1 to 150.
  • * indicates a bond to a carbonate group.
  • the polyol component further contains a compound (A-2) represented by the following formula (A-2) and a compound (A-3) represented by the following formula (A-3).
  • the urethane resin according to [17] or [18].
  • R 1 and R 2 have the same meanings as described above, and n 2 indicates an integer of 1 or more. When n 2 is 2 or more, a plurality of R 2s may be the same or different from each other.
  • R 1 and R 2 have the same meanings as described above, and n 3 , m 3 and p 3 each indicate an integer of 1 or more.
  • a plurality of R 2s may be the same or different from each other. ]
  • the total number of moles of the group represented by the following formula (a-1) contained in the polyol component is defined as CA1
  • the total number of moles of the group represented by the following formula (I) contained in the polyol component is defined as CA1.
  • the urethane resin according to any one of [17] to [19], wherein the molar ratio ( CA1 / CT ) is 0.10 to 0.99.
  • * indicates a bond to a carbonate group.
  • R 1 is synonymous with the above, and * indicates a bond. ]
  • the present invention it is possible to provide a novel polycarbonate polyol and a method for producing the same, which are useful as raw materials for urethane resins and the like, and urethane resins using the polycarbonate polyol as a raw material. According to the present invention, it is also possible to provide a composition containing the polycarbonate polyol, a method for producing the same, and a urethane resin using the composition as a raw material. According to the present invention, it is also possible to provide a composition which has good tensile strength, elongation and texture and contributes to the formation of a urethane resin having excellent durability.
  • a composition which is excellent in handleability, has good elongation and texture, and contributes to the formation of a urethane resin having excellent durability According to the present invention, it is also possible to provide an aqueous urethane resin dispersion containing the urethane resin having an acidic group.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of a composition containing the polycarbonate polyol obtained in Example 2A.
  • FIG. 2 is an enlarged view of 3.430 ppm or more and less than 3.550 ppm in the 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 2A.
  • FIG. 3 is an enlarged view of 3.725 ppm or more and 3.800 ppm or less in the 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 2A.
  • FIG. 4 is a diagram showing a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1B.
  • FIG. 5 is a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1B, which is an enlarged view of 3.430 ppm or more and 3.530 ppm or less.
  • FIG. 6 is a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1B, which is an enlarged view of 3.720 ppm or more and 3.800 ppm or less.
  • FIG. 7 is a diagram showing a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1C.
  • FIG. 8 is a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1C, which is an enlarged view of 3.450 ppm or more and 3.530 ppm or less.
  • FIG. 9 is a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1C, which is an enlarged view of 3.720 ppm or more and 3.800 ppm or less.
  • the numerical range indicated by using “-” indicates a range including the numerical values before and after “-” as the minimum value and the maximum value, respectively.
  • the minimum or maximum value of the numerical range indicated by “" can be arbitrarily combined with the maximum or minimum value of other numerical ranges indicated by “!.
  • the upper limit value and the lower limit value described individually can be arbitrarily combined.
  • the polycarbonate polyol of one embodiment is a compound represented by the following formula (A-1) (hereinafter, also referred to as “compound (A-1)”).
  • A-1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 represents an alkanediyl group
  • n and m each represent an integer of 1 or more.
  • a plurality of R 2s may be the same or different from each other.
  • the alkyl group and hydroxyalkyl group represented by R 1 may be linear or branched.
  • the number of carbon atoms of the alkyl group and the hydroxyalkyl group is, for example, 1 to 5, and may be 1 to 4 or 1 to 2.
  • Specific examples of the alkyl group and the hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, a hydroxybutyl group and the like.
  • R 1 is preferably an alkyl group or a hydroxyalkyl group, and more preferably an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms.
  • the alkanediyl group represented by R2 may be linear or branched. When two or more kinds of R2 are present, all of them may be a linear alkanediyl group or a branched alkanediyl group, some of them are linear alkanediyl groups, and the other part is a branched alkanediyl group. May be.
  • the number of carbon atoms of the alkanediyl group is, for example, 2 to 10.
  • alkanediyl group examples include an ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanjiyl group, a 1,3-butanjiyl group, a 1,4-butandyl group, and 1 , 5-Pentandyl group, 2,2-dimethyl-1,3-propanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentandyl group, 1,8-octanediyl group, 2-ethyl Examples thereof include a -1,6-hexanediyl group, a 1,9-nonandyl group, a 2-methyloctane-1,8-diyl group, a 2-butyl-2-ethyl-1,3-propanediyl group and the like.
  • N and m may be 1 to 65, respectively, and may be 2 to 60 or 2 to 55, respectively.
  • the number average molecular weight of compound (A-1) is, for example, 200 to 6000.
  • the number average molecular weight is a bifunctional polyoxypropylene polyol-equivalent number average molecular weight measured using GPC (Gel Permeation Chromatography).
  • the hydroxyl value of compound (A-1) is, for example, 30 to 800 mgKOH / g.
  • the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of compound (A-1), and is measured according to JIS K1557-1.
  • the properties of compound (A-1) are not particularly limited and may be solid at 25 ° C. or liquid at 25 ° C.
  • Compound (A-1) may be a liquid at a low temperature (for example, 5 ° C.).
  • the properties of compound (A-1) can be changed depending on the type of alkanediyl group contained as R2 in compound (A-1) (number of carbon atoms, presence / absence of branching, etc.), hydroxyl value of compound (A-1), and the like. Is.
  • the compound (A-1) when a plurality of alkanediyl groups are present, when the alkanediyl group is branched, and when the hydroxyl value of the compound (A-1) is high, the compound (A-1) is liquid at 25 ° C. It is easy to become.
  • compound (A-1) contains only a linear alkanediyl group as R 2 . That is, all of R 2 are linear alkanediyl groups. Since the compound (A-1) contains only a linear alkanediyl group as R 2 , it tends to become a solid at 25 ° C.
  • compound (A-1) preferably contains only one linear alkanediyl group as R 2 . In this case, the tendency of compound (A-1) to become a solid at 25 ° C. increases.
  • the carbon number of the linear alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and even more preferably 4 to 9.
  • Preferred examples of the linear alkanediyl group are 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group and 1,9-nonandiyl group.
  • the number average molecular weight of the compound (A-1) of the first embodiment is preferably 200 to 6000, and may be 300 to 5000 or 500 to 4000.
  • the hydroxyl value of the compound (A-1) of the first embodiment is preferably 30 to 800 mgKOH / g, and may be 40 to 700 mgKOH / g or 50 to 600 mgKOH / g.
  • the compound (A-1) contains two or more alkanediyl groups as R2 . Since the compound (A-1) contains two or more alkanediyl groups as R 2 , it tends to become a liquid at 25 ° C.
  • the compound (A-1) is used from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having good tensile strength, elongation and texture and excellent durability is easily formed. It is preferable that R 2 contains only a linear alkanediyl group.
  • An example of a preferred combination of alkanediyl groups is a combination of two or more types of alkanediyl groups having 2 to 10 carbon atoms.
  • a more preferred combination of alkanediyl groups is of 1,6-hexanediol and at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol and 1,9-nonanediol. It is a combination.
  • the compound (A-1) is R in the compound (A-1) from the viewpoint that when it is used as a raw material for a urethane resin, a urethane resin having good tensile strength, elongation and texture and excellent durability is easily formed.
  • the ratio of the number of moles of 1,6-hexanediyl group to the total number of moles of alkanediyl group contained as 2 is preferably 0.30 or more (for example, 0.30 to 0.95), preferably 0.40 or more. It is more preferably (for example, 0.40 to 0.95), and further preferably 0.50 or more (for example, 0.50 to 0.90 or 0.50 to 0.80).
  • the number average molecular weight of the compound (A-1) of the second embodiment is preferably 200 to 6000, and may be 300 to 5000 or 500 to 4000.
  • the hydroxyl value of the compound (A-1) of the second embodiment is preferably 30 to 800 mgKOH / g, and may be 40 to 700 mgKOH / g or 50 to 600 mgKOH / g.
  • compound (A-1) contains a branched alkanediyl group as R2 . Since the compound (A-1) of the third embodiment contains a branched alkanediyl group as R 2 , it tends to become a liquid at 25 ° C.
  • the compound (A-1) may contain two or more alkanediyl groups as R2 . All of the two or more kinds of alkanediyl groups may be branched alkanediyl groups, but when used as a raw material for urethane resin, they have excellent handleability, good elongation and texture, and durability. From the viewpoint that a urethane resin having excellent properties is easily formed, it is preferable that a part of the urethane resin is a linear alkanediyl group.
  • the ratio of the number of moles of the branched alkanediyl group to the total number of moles of the alkanediyl group contained as R2 in the compound (A-1) is preferably 0.10 to 1, preferably 0.20 to 1. It is more preferably 0.90, and even more preferably 0.30 to 0.70.
  • the number of carbon atoms of the branched alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and even more preferably 4 to 9.
  • the number of carbon atoms in the main chain of the branched alkanediyl group is preferably 2 to 9, more preferably 3 to 9, and even more preferably 4 to 8.
  • Preferred examples of the branched alkanediyl group are 3-methylpentane-1,5-diyl group and 2-methyl-1,8-octanediyl group.
  • the carbon number of the linear alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and even more preferably 4 to 9.
  • Preferred examples of the linear alkanediyl group are 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group and 1,9-nonandiyl group.
  • the compound (A-1) when used as a raw material for a urethane resin, is excellent in handleability, good elongation and texture, and easy to form a urethane resin having excellent durability.
  • the ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as R2 is preferably 0 or more (for example, 0 to 0.95), and is preferably 0.10 or more (for example, 0 to 0.95). It is more preferably 0.10 to 0.95), further preferably 0.3 or more (for example, 0.3 to 0.90), and 0.50 or more (for example, 0.50 to 0.80). Is particularly preferable.
  • the number average molecular weight of the compound (A-1) of the third embodiment is preferably 200 to 6000, and may be 300 to 5000 or 500 to 4000.
  • the hydroxyl value of the compound (A-1) of the third embodiment is preferably 30 to 800 mgKOH / g, and may be 40 to 700 mgKOH / g or 50 to 600 mgKOH / g.
  • the polycarbonate polyol (compound (A-1)) described above is, for example, a polyhydric alcohol represented by the following formula (B) (hereinafter, also referred to as “polyhydric alcohol (B)”) and the following formula (D).
  • a polyhydric alcohol represented by the following formula (B) hereinafter, also referred to as “polyhydric alcohol (B)”
  • diol (D) diol
  • two of the hydroxy groups of the polyhydric alcohol (B) are the carbonate.
  • it is obtained by reacting with a reaction product of a carbonate ester and a diol (D).
  • R 1 has the same meaning as described above.
  • R 2 has the same meaning as described above. ]
  • polyhydric alcohol (B) examples include trimethylolpropane, trimethylolethane and pentaerythritol. These may be used alone or in combination of two or more.
  • diol (D) examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1, 5-Pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 2-ethyl-1,6 -Hexanediol, 1,9-nonanediol, 2-methyloctane-1,8-diol and 2-butyl-2-ethyl-1,3-propanediol can be mentioned. These may be used alone or in combination of two or more.
  • Examples of the carbonic acid ester include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate and the like. These may be used alone or in combination of two or more. From the viewpoint of easy availability, easy setting of conditions for the polymerization reaction, etc., it is preferable to use at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, diphenyl carbonate, dibutyl carbonate and ethylene carbonate.
  • At least one of the hydroxy groups of the compound (A-1) is, for example, an unreacted hydroxy group of the hydroxy group derived from the polyhydric alcohol (B) (hydroxy group of the polyhydric alcohol (B)). ).
  • the hydroxy group tends to have lower reactivity than the hydroxy group derived from the diol (D) due to the influence of steric hindrance.
  • the length from the hydroxyl group derived from the polyhydric alcohol (B) to the branch (carbon atom bonded to R 1 ) is shorter than the length from the hydroxy group derived from the diol (D) to the branch. Therefore, the urethane resin obtained by the reaction of the compound (A-1) with the isocyanate compound tends to have higher rigidity.
  • the compound (A-1) is expected to be used as a raw material for various urethane resins by utilizing the difference in the reactivity of the hydroxy group and the length until the branching of the hydroxy group.
  • composition of one embodiment contains the polycarbonate polyol (compound (A-1)) of the above embodiment and the polyhydric alcohol (B).
  • the polyhydric alcohol (B) has the same meaning as described above, and the alkanediyl group possessed by the polyhydric alcohol (B) as R 2 is the same as the alkanediyl group possessed by the compound (A-1) as R 2 . good.
  • the polyhydric alcohol (B) contained in the composition may be two or more.
  • the combination of the alkanediyl groups contained as R 2 in the two or more polyhydric alcohols (B) may be the same as the combination of the alkanediyl groups contained as R 2 in the compound (A-1).
  • the molar ratio ( CA1 / CB ) may be 0.1 to 150.
  • the molar ratio ( CA1 / CB ) is in the above range, when the composition is used as a raw material for a urethane resin, the elongation rate and texture are good, and a urethane resin having excellent durability tends to be easily formed. There is. [In formula (a-1), * indicates a bond to a carbonate group (-OC (O) O-).
  • the molar ratio ( CA1 / CB) is, for example, 1 H - NMR measurement of the composition using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, and 1 H obtained by the measurement.
  • -It can be obtained from the integrated value of the signal in the NMR spectrum. Specifically, for example, the integrated value ⁇ S1 (2 mol of hydrogen atom) of the methylene signal (S1) located next to the hydroxy group of the group represented by the formula (a-1) and the polyvalent alcohol (2 mol of hydrogen atom).
  • the molar ratio ( CA1 / CB) can be calculated from the integrated value ⁇ S2 (hydrogen atom 6 mol) of the methylene signal (S2) located next to the hydroxy group of B ).
  • the molar ratio ( CA1 / CB ) is three times the ratio of the integral value ⁇ S1 of the signal ( S1 ) and the integral value ⁇ S2 of the signal ( S2 ) (3 ⁇ ⁇ S1 / ⁇ S2 ). It can be rephrased.
  • the composition includes a polycarbonate polyol represented by the following formula (A-2) (hereinafter referred to as "compound (A-2)”) and a polycarbonate polyol represented by the following formula (A-3) (hereinafter referred to as "" Compound (A-3) ”) may be further contained.
  • A-2 a polycarbonate polyol represented by the following formula (A-2)
  • A-3 a polycarbonate polyol represented by the following formula (A-3)
  • A-3 Compound (A-3)
  • the atom or group contained as R 1 in compound (A-2) may be the same as the atom or group contained as R 1 in compound (A-1).
  • the atom or group contained as R 1 in compound (A-3) may be the same as the atom or group contained as R 1 in compound (A-1).
  • the alkanediyl group contained as R 2 in compound (A-2) may be the same as the alkanediyl group contained as R 2 in compound (A-1).
  • the alkanediyl group contained as R2 in compound (A-3) may be the same as the alkanediyl group contained as R2 in compound (A-1).
  • compound (A-1) contains two or more alkanediyl groups as R 2
  • compound (A-2) and compound (A-3) may also contain two or more alkanediyl groups as R 2 . ..
  • the combination of the alkanediyl groups contained as R 2 in the compound (A-2) and the compound (A-3) is the same as the combination of the alkanediyl groups contained as R 2 in the compound (A-1). It's okay.
  • n 2 , n 3 , m 3 and p 3 may be 1 to 65, respectively, and may be 2 to 60 or 3 to 50, respectively.
  • the total number of moles of the group represented by the above formula (a - 1) contained in the composition is defined as CA1
  • the total number of moles of the polyvalent alcohol contained in the composition is defined as CB
  • the molar ratio ( CA1 / CT ) may be 0.10 to 0.99
  • the molar ratio ( CB / CT) may be 0.10 to 0.99.
  • the molar ratio (CA1 / CT ) and the molar ratio ( CB / CT) are, for example, the same as the molar ratio (CA1 / C B ) , using deuterated chloroform as a solvent and tetramethylsilane.
  • R 1 of the formula (I) is an alkyl group
  • the molar ratio ( CA1 / CT) can be calculated from the ratio of the signal (S3) of the terminal methyl of the above to the integrated value ⁇ S3 (hydrogen atom 3 mol), and the integrated value ⁇ S2 (hydrogen) of the above signal ( S2 ).
  • the molar ratio ( CB / CT ) can be calculated from the ratio of the integrated value ⁇ S3 (hydrogen atom 3 mol) of the signal (S3) to the atom (6 mol content).
  • the molar ratio ( CA1 / CT) is 1.5 times the ratio of the integral value ⁇ S1 of the signal ( S1 ) and the integral value ⁇ S3 of the signal ( S3 ) (1.5 ⁇ ⁇ S1 /).
  • the molar ratio (CB / CT ) is 0.5 times the ratio of the integral value ⁇ S2 of the signal ( S2 ) and the integral value ⁇ S3 of the signal ( S3 ) (0). It can be rephrased as .5 ⁇ ⁇ S2 / ⁇ S3 ).
  • the composition may further contain, for example, the diol (D), the carbonic acid ester, a polycarbonate diol which is a reaction product of the diol (D) and the carbonic acid ester, and the like.
  • the composition preferably contains a compound having a group represented by the above formula (I) (compounds (A-1) to (A-3), polyhydric alcohol (B), etc.) as a main component.
  • the principal component means a component (component group) having the highest mass fraction.
  • the content of the diol (D) may be 20 to 60% by mass based on the total mass of the composition.
  • the content of the carbonic acid ester may be 20 to 60% by mass based on the total mass of the composition.
  • the content of the polycarbonate diol may be 20 to 80% by mass based on the total mass of the composition.
  • the polycarbonate diol that can be contained in the composition is represented by, for example, the following formula (E).
  • R 2 has the same meaning as described above, and q represents an integer of 1 or more (for example, 1 to 60). ]
  • polycarbonate diol (E) When the polycarbonate diol represented by the above formula (E) (hereinafter referred to as "polycarbonate diol (E)") is contained, the proportion of the compound having a large value of q indicating the degree of polymerization in the total amount of the polycarbonate diol (E) is The larger the amount, the better the texture characteristics tend to be. This tendency is that as the ratio of the 1,6-hexanediyl group in the 1,4-butanediyl group, 1,5-pentanediyl group and 1,6-hexanediyl group contained as R2 increases, the polycarbonate diol ( The larger the number average molecular weight of E), the more remarkable it is.
  • the above ratio can be confirmed, for example, by comparing the peaks corresponding to each component of the LC spectrum obtained by LC-MS measurement using reverse phase chromatography. For example, among the peaks observed in the LC spectrum, the maximum intensity of the peak corresponding to the polycarbonate diol (E) having q 3 is P3, and the maximum intensity of the peak corresponding to the polycarbonate diol (E) having q 4 is P3. Is P4, and the maximum intensity of the peak corresponding to the polycarbonate diol (E) having q is P5, the ratio of P3 to the sum of P3, P4 and P5 (P3 / [P3 + P4 + P5]) is 0.1 to.
  • the ratio of P5 to the sum of P3, P4 and P5 is preferably 0.1 to 0.70, more preferably 0.15 to 0.50, and 0.2. It is more preferably ⁇ 0.40.
  • P3 / (P3 + P4 + P5) and P5 / (P3 + P4 + P5) are in the above range, a urethane resin having a particularly good texture tends to be easily formed when the composition is used as a raw material for the urethane resin.
  • MS measurement device: Bruker Daltonics microTOF, ion source: APCI, measurement mode: positive mode
  • MS measurement device: Bruker Daltonics microTOF, ion source: APCI, measurement mode: positive mode
  • the main peak of the obtained spectrum is analyzed. It can be confirmed at.
  • the composition may be a reaction mixture of a polyhydric alcohol (B), a diol (D), and a carbonic acid ester. Since the reaction is usually carried out in the presence of a transesterification catalyst, the composition may further contain a transesterification catalyst. Lithium acetylacetonate is preferably used as the transesterification catalyst. The content of the transesterification catalyst may be 0.0001 to 0.100% by mass based on the total mass of the composition.
  • the properties of the composition are not particularly limited and may be solid at 25 ° C. or liquid at 25 ° C.
  • the composition may be liquid at low temperatures (eg 5 ° C.).
  • the properties of the composition can be changed depending on the type and content ratio of the contained components (for example, compounds (A-1) to (A-3) and the polyhydric alcohol (B)).
  • the number average molecular weight of the composition is, for example, 200 to 6000.
  • the number average molecular weight of the composition is a bifunctional polyoxypropylene polyol-equivalent number average molecular weight measured by using GPC (Gel Permeation Chromatography) for the entire composition as a measurement target.
  • the hydroxyl value of the composition is, for example, 30 to 800 mgKOH / g.
  • the hydroxyl value of the composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the composition, and is measured according to JIS K1557-1.
  • the composition of the first embodiment contains the compound (A-1) of the first embodiment as the compound (A-1).
  • the molar ratio ( CA1 / CB ) is, for example, 0.2 to 150.
  • the composition of the first embodiment having such characteristics tends to become a solid at 25 ° C.
  • the above signal (S1) is 1 H.
  • the above signal (S2) is 3.725 ppm or more and 3.800 ppm or less (or 3.725 ppm or more and less than 3.800 ppm) of 1 H-NMR spectrum. Observed in the range of.
  • the signal (S3) is observed in the range of 0.700 ppm or more and 1.000 ppm or less, and when R 1 of the formula (I) is a methyl group.
  • the signal (S3) is observed in the range of 0.700 ppm or more and 1.130 ppm or less. Therefore, in the first embodiment, the molar ratio ( CA1 / CB ), the molar ratio ( CA1 / CT ), and the molar ratio ( CB / CT ) are obtained from the ratio of the integrated values of these signals. Can be done.
  • the molar ratio ( CA1 / CB) in the composition of the first embodiment is preferably 0.500 or more, more preferably 3.000 or more, still more preferably 5.000 or more.
  • the molar ratio ( CA1 / CB ) is preferably 120 or less, more preferably 90 or less, still more preferably 60 or less.
  • the molar ratio ( CA1 / CT ) in the composition of the first embodiment is, for example, 0.12 to 0.99.
  • the molar ratio ( CA1 / CT) may be 0.150 or more or 0.200 or more, and may be 0.800 or less or 0.500 or less.
  • a urethane resin having good tensile strength, elongation and texture and excellent durability is formed. Tends to be easy to do.
  • the molar ratio ( CB / CT) in the composition of the first embodiment is, for example, 0.001 to 0.900 .
  • the molar ratio ( CB / CT) may be 0.003 or more or 0.005 or more, and may be 0.300 or less or 0.100 or less.
  • the molar ratio ( CB / CT ) is in the above range, when the composition is used as a raw material for a urethane resin, a urethane resin having good tensile strength, elongation and texture and excellent durability is formed. Tends to be easy to do.
  • the ratio ( ⁇ S1 / ⁇ S2) of the integrated value ⁇ S1 of the signal ( S1 ) to the integrated value ⁇ S2 of the signal ( S2 ) is, for example, 0.067 to 50.
  • the above ratio ( ⁇ S1 / ⁇ S2 ) may be 0.500 or more, 1.000 or more, or 2.000 or more, and may be 40 or less, 30 or less, or 20 or less.
  • the ratio ( ⁇ S1 / ⁇ S3) of the integrated value ⁇ S1 of the signal (S1) to the integrated value ⁇ S3 of the signal ( S3 ) is, for example, 0.08 to 0.66.
  • the above ratio ( ⁇ S1 / ⁇ S3 ) may be 0.100 or more or 0.133 or more, and may be 0.533 or less or 0.333 or less.
  • the ratio ( ⁇ S2 / ⁇ S3 ) of the integrated value ⁇ S2 of the signal ( S2 ) to the integrated value ⁇ S3 of the signal ( S3 ) is, for example, 0.002 to 1.8.
  • the above ratio ( ⁇ S2 / ⁇ S3 ) may be 0.006 or more or 0.010 or more, and may be 0.600 or less or 0.200 or less.
  • the composition of the second embodiment contains the compound (A-1) of the second embodiment as the compound (A-1).
  • the molar ratio ( CA1 / CB ) is, for example, 0.1 to 150.
  • the composition of the second embodiment having such characteristics tends to become a liquid at 25 ° C.
  • the above signal (S1) is 1 H.
  • the above signal (S2) is 3.720 ppm or more and 3.800 ppm or less (or 3.720 ppm or more and less than 3.800 ppm) in 1 H-NMR spectrum. Observed in the range of.
  • the signal (S3) is observed in the range of 0.700 ppm or more and 1.000 ppm or less, and when R 1 of the formula (I) is a methyl group.
  • the signal (S3) is observed in the range of 0.700 ppm or more and 1.130 ppm or less. Therefore, in the second embodiment, the molar ratio ( CA1 / CB ), the molar ratio ( CA1 / CT ), and the molar ratio ( CB / CT ) are obtained from the ratio of the integrated values of these signals. Can be done.
  • the molar ratio ( CA1 / CB ) in the composition of the second embodiment is preferably 0.100 or more, more preferably 3.000 or more, still more preferably 5.000 or more.
  • the molar ratio ( CA1 / CB ) is preferably 150 or less, more preferably 90 or less, still more preferably 60 or less.
  • the molar ratio ( CA1 / CT ) in the composition of the second embodiment is, for example, 0.10 to 0.99.
  • the molar ratio ( CA1 / CT) may be 0.200 or more or 0.300 or more, and may be 0.800 or less or 0.600 or less.
  • a urethane resin having good tensile strength, elongation and texture and excellent durability is formed. Tends to be easy to do.
  • the molar ratio ( CB / CT) in the composition of the second embodiment is, for example, 0.001 to 0.900 .
  • the molar ratio (CB / CT ) may be 0.005 or more or 0.010 or more, and may be 0.300 or less or 0.100 or less.
  • the molar ratio ( CB / CT ) is in the above range, when the composition is used as a raw material for a urethane resin, a urethane resin having good tensile strength, elongation and texture and excellent durability is formed. Tends to be easy to do.
  • the ratio ( ⁇ S1 / ⁇ S2) of the integrated value ⁇ S1 of the signal (S1) to the integrated value ⁇ S2 of the signal ( S2 ) is, for example, 0.030 to 50.
  • the above ratio ( ⁇ S1 / ⁇ S2 ) may be 0.500 or more, 1.000 or more, or 2.000 or more, and may be 40 or less, 30 or less, or 20 or less.
  • the ratio ( ⁇ S1 / ⁇ S3) of the integrated value ⁇ S1 of the signal ( S1 ) to the integrated value ⁇ S3 of the signal ( S3 ) is, for example, 0.067 to 0.66.
  • the above ratio ( ⁇ S1 / ⁇ S3 ) may be 0.133 or more or 0.200 or more, and may be 0.533 or less or 0.400 or less.
  • the ratio ( ⁇ S2 / ⁇ S3 ) of the integrated value ⁇ S2 of the signal ( S2 ) to the integrated value ⁇ S3 of the signal ( S3 ) is, for example, 0.002 to 1.800.
  • the above ratio ( ⁇ S2 / ⁇ S3 ) may be 0.010 or more or 0.020 or more, and may be 0.6 or less or 0.2 or less.
  • the composition of the third embodiment contains the compound (A-1) of the third embodiment as the compound (A-1).
  • the molar ratio ( CA1 / CB ) is, for example, 0.1 to 150.
  • the composition of the third embodiment having such characteristics tends to become a liquid at 25 ° C.
  • the above signal (S1) is 1 H.
  • the above signal (S2) is 3.720 ppm or more and 3.800 ppm or less (or 3.720 ppm or more and less than 3.800 ppm) in 1 H-NMR spectrum. Observed in the range of. Therefore, in the third embodiment, the molar ratio ( CA1 / CB ) can be obtained from the ratio of the integrated values of these signals.
  • the molar ratio ( CA1 / CB ) in the composition of the third embodiment is preferably 0.100 or more, more preferably 1.000 or more, still more preferably 2.000 or more.
  • the molar ratio ( CA1 / CB ) is preferably 120 or less, more preferably 90 or less, still more preferably 60 or less.
  • the ratio ( ⁇ S1 / ⁇ S2) of the integrated value ⁇ S1 of the signal (S1) to the integrated value ⁇ S2 of the signal ( S2 ) is, for example, 0.033 to 50.
  • the above ratio ( ⁇ S1 / ⁇ S2 ) may be 0.500 or more, 1.000 or more, or 2.000 or more, and may be 40 or less, 30 or less, or 20 or less.
  • the composition of the above embodiment can also be obtained as a reaction mixture containing the compound (A-1). Therefore, the above method can be referred to as a method for producing the composition of the above embodiment.
  • the details of the polyhydric alcohol (B), the diol (D) and the carbonic acid ester are as described above, and suitable examples thereof (examples of preferable R 1 and R 2 and examples of preferable combinations) are also compound (A). It is the same as the preferable example of R 1 and R 2 and the example of the preferable combination of -1).
  • the transesterification catalyst it is preferable to use lithium acetylacetonate from the viewpoint that the desired compound (A-1) can be easily obtained.
  • the ratio of the number of moles of 1,6-hexanediol to the total number of moles of D) is preferably 0.30 or more (for example, 0.30 to 0.95), preferably 0.40 or more (for example, 0.40 to 0.40 to). It is more preferably 0.95), and further preferably 0.50 or more (for example, 0.50 to 0.90 or 0.50 to 0.80).
  • the mixing ratio of the polyhydric alcohol (B) and the diol (D) (the content of the diol (D) in the mixed solution / the content of the polyhydric alcohol (B) in the mixed solution) is 1 / in terms of molar ratio. It is preferably 100 to 5/1, more preferably 1/80 to 3/1. By setting the mixing ratio of the diol and the polyhydric alcohol within the above range, the compound (A-1) can be efficiently obtained.
  • the mixing ratio may be 1/5 to 60/1 or 1/1 to 40/1 in terms of molar ratio.
  • Mixing ratio of carbonic acid ester and polyhydric alcohol (B) and diol (D) (total content of carbonic acid ester in the mixed solution / total content of polyhydric alcohol (B) and diol (D) in the mixed solution) Is preferably 1/3 to 3/1, more preferably 1 / 2.5 to 2.5 / 1, in terms of molar ratio.
  • the content of the transesterification catalyst in the mixed solution is such that the reaction temperature can be easily controlled appropriately and the increase in the number of colors of the reaction product can be suppressed.
  • the total amount may be 0.0001 to 0.1 parts by mass and 0.0005 to 0.01 parts by mass with respect to 100 parts by mass.
  • the content of the transesterification catalyst is preferably as small as possible from the viewpoint of facilitating the control of the reactivity of the urethanization reaction. As the content of the transesterification catalyst increases, the reactivity of the urethanization reaction tends to increase.
  • the content of the transesterification catalyst in the mixed solution is 0.001 mass by mass with respect to 100 parts by mass of the total amount of the polyhydric alcohol, the diol and the carbonic acid ester in the mixed solution from the viewpoint of facilitating the reaction control of urethanization.
  • the amount is preferably 0.002 parts by mass or more, more preferably 0.002 parts by mass or more, and further preferably 0.003 parts by mass or more.
  • the content of the ester exchange catalyst in the mixed solution is 0 with respect to 100 parts by mass of the total amount of the polyhydric alcohol, the diol and the carbonic acid ester in the mixed solution from the viewpoint of suppressing the increase in the number of colors of the reaction product.
  • the content of the transesterification catalyst in the mixed solution is 0.001 to 0.050 parts by mass with respect to 100 parts by mass of the total amount of the polyhydric alcohol, the diol and the carbonic acid ester in the mixed solution. It is preferably 0.002 to 0.040 parts by mass, more preferably 0.003 to 0.030 parts by mass.
  • the heating temperature (reaction temperature) of the mixed solution is, for example, 80 to 250 ° C., and may be 100 to 220 ° C.
  • reaction temperature 80 ° C. or higher
  • the transesterification reaction easily proceeds and the desired compound (A-1) can be easily obtained.
  • reaction temperature 250 ° C. or lower
  • the number of colors of the obtained compound (A-1) and the composition polyol can be suppressed.
  • the transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while raising the temperature stepwise or continuously depending on the progress of the reaction.
  • heating is performed at a temperature T1 satisfying the relationship of the following formula ( ⁇ ), and then at a temperature T2 satisfying the relationship of the following formula ( ⁇ ). It is preferable to perform heating. It is preferable that the temperature T1 and the temperature T2 satisfy the relationship of the following formula ( ⁇ ). Further, it is preferable that the average temperature T1 m of the first heating temperature and the average temperature T2 m of the second heating temperature satisfy the relationship of the following formula ( ⁇ ).
  • the extent of reaction can be estimated from the distillate amount of the distillate. 120 ° C ⁇ T1 ⁇ 155 ° C ... ( ⁇ ) 140 ° C ⁇ T2 ⁇ 155 ° C ... ( ⁇ ) T1 ⁇ T2 ... ( ⁇ ) T1 m ⁇ T2 m ... ( ⁇ )
  • the mixed solution can be heated under normal pressure, but in the latter half of the reaction, it can also be heated under reduced pressure (for example, under a pressure of 101 to 0.1 kPa). As a result, the distilling speed of the generated distillate can be increased, and the progress of the reaction can be accelerated.
  • the normal pressure means a pressure of 101.325 kPa ⁇ 20.000 kPa. From the viewpoint of facilitating the acquisition of the desired compound (A-1), the mixed solution is heated under a pressure of 101.325 kPa ⁇ 20.000 kPa (first heating), followed by 10.000 kPa or less.
  • the temperature of the first heating is the temperature T1 satisfying the relationship of the above formula ( ⁇ ), and the temperature of the second heating is the above. It is more preferable that the temperature T2 satisfies the relationship of the formula ( ⁇ ), and the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula ( ⁇ ). Is even more preferable. Further, from the viewpoint of making it easier to obtain the compound (A-1), it is preferable to distill off the alcohol derived from the carbonic acid ester at 120 ° C. or lower and remove it from the reaction system.
  • the obtained reaction mixture may be subjected to post-treatment such as distillation and drying. Further, in the above-mentioned production method, after obtaining the compound (A-1) or a composition containing the compound (A-1), a component such as a polyhydric alcohol (B) is added to the composition of the above-described embodiment (for example, the above-mentioned mole). Compositions satisfying the ratio ( CA1 / CB ), molar ratio ( CA1 / CT ) and molar ratio ( CB / CT )) may be prepared.
  • the urethane resin is a polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof.
  • the crosslinked product means a product in which polycondensates are crosslinked with each other by a chain extender or the like.
  • the polyol component contains the above compound (A-1).
  • the polyol component may contain a polyol (a compound having two or more terminal hydroxyl groups) other than the compound (A-1).
  • the polyol component further contains, for example, a polyol (compound (A-2), compound (A-3), polyhydric alcohol (B), diol (D), polycarbonate diol, etc.) that can be contained in the above composition. May be good.
  • the content ratio of these polyols is the content ratio of the polyol in the above composition (for example, molar ratio ( CA1 / CB ), molar ratio ( CA1 / CT ) and molar ratio ( CB / CT )). It may be the same.
  • the polyol component may contain a polyol mixture obtained by removing compounds other than the polyol from the above composition.
  • the polyol component may further contain a polyol having an acidic group.
  • the urethane resin contains an acidic group.
  • a urethane resin having an acidic group is preferably used for an aqueous urethane resin dispersion. The aqueous urethane resin dispersion will be described later.
  • the acidic group is, for example, a functional group (hydrophilic group) capable of imparting hydrophilicity to the isocyanate group-terminated prepolymer obtained by reaction with isocyanate.
  • a functional group hydrophilic group
  • examples of the polyol having such an acidic group include dimethylolalkanoic acid such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), trimethylolpentanoic acid, and dimethylolnonenic acid.
  • polyisocyanate examples include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates and alicyclic polyisocyanates. Further, modified polyisocyanate which is a modified product thereof can also be used. Examples of the modified polyisocyanate include isocyanurate-modified polyisocyanate (isocyanate trimer), allophanate-modified polyisocyanate, uretdione-modified polyisocyanate, urethane-modified polyisocyanate, biuret-modified polyisocyanate, uretonimine-modified polyisocyanate, and acylurea-modified polyisocyanate. And so on. These can be used alone or in combination of two or more.
  • aromatic isocyanate examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate / 2,6-tolylene diisocyanate mixture, 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate / 4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl-terldiisocyanate, 2-nitrodiphenyl -4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropanediiso
  • aromatic aliphatic isocyanate examples include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and mixtures thereof; 1,3-bis (1-isocyanato-1-methylethyl) benzene, 1,4-. Bis (1-isocyanato-1-methylethyl) benzene and mixtures thereof; ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene and the like can be mentioned.
  • aliphatic isocyanate examples include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, and trimethylene.
  • alicyclic isocyanate examples include isophorone diisocyanate, cyclohexyldiisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyldiisocyanate, dicyclohexyldimethylmethanediisocyanate, 2,2'-dimethyldicyclohexylmethanediisocyanate, and bis (4-isocyanato).
  • the molar ratio of the active hydrogen in the polyol component to the isocyanate group in the polyisocyanate component is preferably 9: 1 to 1: 9, preferably 6: 4 to 4. : 6 is more preferable.
  • the compounding ratio is within this range, the urethane resin tends to have better performance.
  • the chain extender can be appropriately selected depending on the purpose, use and the like.
  • Examples of the chain extender include water; ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, and 1,10-decane.
  • High polymer polyols such as polyesterpolyol, polyesteramide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, and polyolefin polyol; ethylenediamine, isophoronediamine, 2-methyl-1,5-pentanediamine, aminoethylethanol.
  • Polyamines such as amine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine can be used.
  • the blending amount of the chain extender ratio of the structure derived from the chain extender contained in the urethane resin
  • the chain extender is a polyol, the content of the polyol is calculated assuming that it is included in both the chain extender and the polyol component.
  • the urethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and a chain extender in some cases (urethaneization reaction).
  • the urethanization reaction may be carried out at room temperature (eg, 25 ° C.) or under heating (eg, 40-150 ° C.).
  • a catalyst (urethanization catalyst) can be added for the purpose of shortening the reaction time, improving the reaction rate, and the like.
  • the catalyst include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and tin-based catalysts such as stanas octoate, stanas oleate, and dibutyltin dilaurate.
  • metal catalysts such as. These can be used alone or in combination of two or more. Among these, dibutyl tin dilaurate is preferably used.
  • the amount of the catalyst used may be 0.001 to 100 parts by mass with respect to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.
  • a phosphorus compound for treating the catalyst.
  • the phosphorus compound is not particularly limited, and is, for example, a phosphate triester such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl / diphenyl phosphate; methyl acid phosphate.
  • acidic phosphoric acid ester is preferable, and 2-ethylhexyl acid phosphate is more preferable.
  • the amount of the phosphorus compound used may be 10 to 2000 parts by mass with respect to 100 parts by mass of the catalyst.
  • the urethanization reaction can be carried out in the presence of a solvent.
  • a solvent examples include esters such as ethyl acetate, butyl acetate, propyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone and ⁇ -caprolactone; amides such as dimethylformamide, diethylformamide and dimethylacetamide; and sulfoxides such as dimethylsulfoxide.
  • Esters such as tetrahydrofuran, dioxane, 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene and toluene can be used.
  • the urethane resin described above has good elongation and texture, excellent durability, and in some cases, good tensile strength. Therefore, the urethane resin can be suitably used for synthetic leather, artificial leather, coating materials and the like.
  • the aqueous urethane resin dispersion contains an aqueous medium and a urethane resin or a neutralized product thereof dispersed in the aqueous medium.
  • the urethane resin is one of the above-mentioned urethane resins having an acidic group (the polyol component contains a polyol having an acidic group).
  • the water-based medium in addition to water, a solution containing an emulsifier, a dispersant, etc. can be used.
  • the water-based medium preferably contains water, and more preferably consists only of water.
  • the acidic group of the urethane resin may be neutralized by the neutralizing agent.
  • the neutralizing agent include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, and morpholine.
  • N-Methylmorpholine 2-amino-2-ethyl-1-propanol
  • organic amines such as higher alkyl-modified morpholine
  • alkali metals such as lithium, potassium and sodium
  • inorganic alkalis such as sodium hydroxide and potassium hydroxide.
  • a highly volatile neutralizing agent that easily dissociates by heating such as ammonia, trimethylamine, and triethylamine is preferably used.
  • These neutralizers can be used alone or in combination of two or more.
  • an anionic polar group-containing compound can also be used.
  • the anionic polar group-containing compound include those composed of an organic acid having one or more active hydrogens and a neutralizing agent.
  • the organic acid include carboxylate, sulfonate, phosphate, phosphonate, phosphinate, thiosulfonate and the like. These anionic polar groups contained in the organic acid may be introduced alone or may be associated with a metal ion such as a chelate.
  • a cationic polar group-containing compound in producing the aqueous urethane resin dispersion, a cationic polar group-containing compound can also be used.
  • the cationic polar group-containing compound for example, one selected from the group consisting of a tertiary amine having one or more active hydrogens, an inorganic acid neutralizing agent, an organic acid neutralizing agent, and a quaternary agent. It consists of.
  • a cationic compound such as a primary amine salt, a secondary amine salt, a tertiary amine salt and a pyridinium salt can also be used.
  • tertiary amine having one or more active hydrogens examples include N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dipropylethanolamine, N, N-diphenylethanolamine, and N-.
  • a primary amine such as
  • Examples of the inorganic acid and the organic acid include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid and sulfuric acid.
  • quaternary agent examples include dimethyl sulfate, benzyl chloride, bromoacetamide, chloroacetamide and the like. Further, alkyl halides such as ethyl bromide, propyl bromide and butyl bromide can also be used.
  • the aqueous urethane resin dispersion is prepared by, for example, reacting a polyol component containing a polyol having an acidic group with a polyisocyanate component in the presence of a solvent or in the absence of a solvent to obtain a urethane prepolymer.
  • a catalyst can be used as needed to promote the reaction and control the amount of by-products.
  • the film formed by the aqueous urethane resin dispersion described above (for example, the film formed by coating the aqueous urethane resin dispersion on the substrate) is excellent in adhesion, flexibility, tactile sensation and the like. Therefore, the aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather and coating materials.
  • the polyol component and polyisocyanate component for forming the urethane resin may be stored, transported, etc. in separate containers as a two-component composition set.
  • the two-component composition set contains at least a first liquid containing the polyol component and a second liquid containing at least the polyisocyanate component.
  • a chain extender, a catalyst, a solvent or the like When a chain extender, a catalyst, a solvent or the like is used, these may be contained in the first liquid and / or the second liquid, and may be blended separately from the first liquid and the second liquid.
  • the above-mentioned two-component composition set can be suitably used as a coating material, for example, and can also be suitably used in the production of artificial leather, synthetic leather and the like.
  • the above two-component composition set is used as a coating material, for example, after mixing the first solution and the second solution, the obtained mixed solution is applied onto a substrate and, in some cases, heated to apply the mixture.
  • a film for example, a cured film containing a urethane resin
  • Example 1A Trimethylolpropane 35.2 g, 1,4-butanediol 354.2 g, diethyl carbonate 510.7 g, and lithium acetylacetonate in a 1 L double-ended glass reactor with a stirrer, thermometer, heater, and cooler. 0.045 g was mixed. The obtained mixed solution was heated at 130 to 150 ° C. (initial 130 ° C., final stage 150 ° C.) under normal pressure, and reacted for 8 hours while removing low boiling point components (alcohol derived from carbonic acid ester, etc.). The distillate temperature was 77 ° C. or higher and lower than 79 ° C.
  • Example 2A Example 1A and Example 1A except that a mixed solution obtained by mixing 31.3 g of trimethylolpropane, 413.8 g of 1,6-hexanediol, 454.9 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was used. Similarly, a composition (PCP-2A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained.
  • Example 3A Except for the fact that a mixed solution obtained by mixing 83.0 g of trimethylolpropane, 334.6 g of 1,4-butanediol, 482.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was used, the same as in Example 1A. Similarly, a composition (PCP-3A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained.
  • Example 4A Trimethylolpropane 74.4 g, 1,6-hexanediol 393.2 g, diethyl carbonate 432.4 g, and lithium acetylacetonate in a 1 L double-ended glass reactor with a stirrer, thermometer, heater, and cooler.
  • a composition (PCP-4A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1A except that a mixed solution obtained by mixing 0.045 g was used. rice field.
  • Example 5A 900 g of the composition (PCP-2A) obtained in Example 2A and 100 g of trimethylolpropane are mixed at 80 ° C., and a composition containing a polycarbonate polyol represented by the above formula (A-1) (A-1). PCP-5A) was obtained.
  • Example 6A Trimethylolethane 33.6 g, 1,6-hexanediol 198.3 g, diethyl carbonate 218.1 g, and lithium acetylacetonate in a 1 L double-ended glass reactor with a stirrer, thermometer, heater and condenser.
  • a composition (PCP-6A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1A except that a mixed solution obtained by mixing 0.025 g was used. rice field.
  • Example 7A Pentaerythritol 37.7 g, 1,6-hexanediol 196.4 g, diethyl carbonate 215.9 g, and lithium acetylacetonate 0 in a 1 L double-ended glass reactor with a stirrer, thermometer, heater, and cooler.
  • a composition (PCP-7A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1A except that a mixed solution obtained by mixing .025 g was used. ..
  • Example 8A A composition (PCP-8A) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 4A except that the distillate temperature was set to 80 ° C. or higher and lower than 83 ° C. ..
  • Example 9A The above formula (A-1) is the same as in Example 4A, except that the blending amount of lithium acetylacetonate is changed to 0.135 g and the distillate temperature is set to 84 ° C. or higher and lower than 108 ° C. A composition containing a polycarbonate polyol represented by (PCP-9A) was obtained.
  • Example 2A Same as Example 1A except that a mixed solution obtained by mixing 74.4 g of trimethylolpropane, 393.2 g of 1,6-hexanediol, 432.4 g of diethyl carbonate, and 0.09 g of tetrabutyl titanate was used. A composition containing a polycarbonate polyol (PCP-14A) was obtained.
  • PCP-14A polycarbonate polyol
  • composition analysis (1) The composition of the composition was analyzed by the following procedure.
  • the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Wako Pure Chemical Industries, Ltd.) to obtain a solution.
  • Tetramethylsilane (TMS) was added to the solution as a chemical shift reference to obtain a test solution.
  • 1 H-NMR was measured using JNM-ECX400 manufactured by JEOL Ltd., and 1 H-NMR spectrum was obtained with the TMS signal as 0 ppm.
  • the 1 H-NMR spectra of the composition obtained in Example 2A are shown in FIGS. 1 to 3. The measurement was performed under the following conditions.
  • a signal of 3.430 ppm or more and less than 3.550 ppm is a signal (S1)
  • a signal of 3.725 ppm or more and 3.800 ppm or less is a signal (S2)
  • a signal of 0.700 ppm or more and 1.130 ppm or less is used.
  • R 1 of the group represented by the formula (I) is a methyl group (when the polyhydric alcohol (B) is trimethylolethane)
  • the signal (S3) is 0.700 ppm or more and 1.000 ppm or less.
  • the signal was taken as the signal (S3) when R 1 of the group represented by the formula (I) was an ethyl group (when the polyhydric alcohol (B) was trimethylolpropane).
  • the baseline for the integrated value measurement was a straight line drawn horizontally with the lower spectral intensity as a reference by comparing the spectral intensities at both ends of the specified spectral range.
  • the molar ratio ( CA1 / CB ), the molar ratio ( CA1 / CT ) and the molar ratio ( CB / CT ) were calculated.
  • the results are shown in Tables 2 and 3.
  • the presence of the compound (A-1) was suggested by the presence of the signal (S1).
  • no signal (S1) was confirmed in PCD-1A and PCP-14A.
  • the presence of the compound (A-2) was suggested by the presence of the signal (S4) of 3.550 ppm or more and 3.62 ppm or less.
  • the three bonds in the formula (I) one is a bond to a carbonate group and two are bonds to a hydroxy group.
  • composition analysis (2) LC-MS measurement of the composition obtained above was carried out under the following conditions, and the maximum intensity P3 of the peak corresponding to the polycarbonate diol having q of 3 in the formula (E) and q in the formula (E).
  • the maximum intensity P4 of the peak corresponding to the polycarbonate diol having a value of 4 and the maximum intensity P5 of the peak corresponding to the polycarbonate diol having a q of 5 in the formula (E) were obtained, and the sum of P3, P4 and P5 was obtained.
  • HPLC methanol Wako Pure Chemical Industries, Ltd.
  • HPLC (4) Pretreatment Weigh the sample (composition) and add the specified mobile phase (Liquid B). The mixture was allowed to stand overnight at room temperature to dissolve it. The obtained sample solution was gently shaken and filtered through a 0.45 ⁇ m PTFE cartridge filter.
  • composition (unit: g) of Examples 1A to 4A and 6A to 9A, Reference Examples 2A to 4A, and Comparative Example 2A indicates reaction raw materials, and Examples 5A and Reference Examples.
  • composition (unit: g) of 1A and Comparative Example 1A indicates a compounding component.
  • a urethane cured film film was prepared by the following method, and the physical properties (tensile properties, moist heat resistance properties, texture properties) were evaluated using the obtained film as a sample.
  • Tensile strength retention rate (%) C / D ⁇ 100 (1)
  • C Tensile strength (MPa) after moisture resistance test
  • D Tensile strength (MPa) before moist heat resistance test When the tensile strength retention rate was 80% or more, it was judged that the moisture and heat resistance characteristics were good.
  • the details of the materials used in the first embodiment are as follows. ⁇ 1,4-Butanediol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ 1,6-hexanediol: manufactured by BASF-JAPAN ⁇ Trimethylol Propane: manufactured by Sigma-Aldrich ⁇ Trimethylol Etan: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ Pentaerythritol: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. ⁇ diethyl carbonate: manufactured by Sigma-Aldrich Co., Ltd. ⁇ Dimethyl carbonate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Lithium acetylacetonate manufactured by Sigma-Aldrich Co., Ltd.
  • Lithium hydroxide Tokyo Chemical Industry Tetrabutyl titanate manufactured by Tokyo Kasei Kogyo Co., Ltd.
  • Example 1B Trimethylolpropane 35.2 g, 1,6-hexanediol 298.5 g, 1,4-butanediol 97.5 g, carbonic acid in a 1 L double-ended glass reactor with a stirrer, thermometer, heater and cooler. 468.8 g of diethyl and 0.045 g of lithium acetylacetonate were mixed. The obtained mixed solution was heated at 130 to 150 ° C. (initial 130 ° C., final stage 150 ° C.) under normal pressure, and reacted for 8 hours while removing low boiling point components (alcohol derived from carbonic acid ester, etc.). The distillate temperature was 77 ° C.
  • Example 2B A mixed solution obtained by mixing 34.6 g of trimethylolpropane, 218.4 g of 1,6-hexanediol, 166.6 g of 1,4-butanediol, 480.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was prepared.
  • a composition (PCP-2B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except that it was used.
  • Example 3B A mixed solution obtained by mixing 75.6 g of trimethylolpropane, 358.2 g of 1,6-hexanediol, 30.4 g of 1,4-butanediol, 426.1 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was prepared.
  • a composition (PCP-3B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except that it was used.
  • Example 4B A mixed solution obtained by mixing 37.3 g of trimethylolpropane, 273.7 g of 1,6-hexanediol, 159.1 g of 1,9-nonanediol, 432.8 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-4B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except that it was used.
  • Example 5B 900 g of the composition (PCP-1B) obtained in Example 1B and 100 g of trimethylolpropane are mixed at 80 ° C., and a composition containing a polycarbonate polyol represented by the above formula (A-1) (PCP-5B). ) was obtained. Obtained.
  • Example 6B A mixed solution obtained by mixing 31.4 g of trimethylolethane, 299.8 g of 1,6-hexanediol, 98.0 g of 1,4-butanediol, 470.8 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was prepared.
  • a composition (PCP-6B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except that it was used.
  • Example 7B A mixed solution obtained by mixing 35.8 g of pentaerythritol, 298.3 g of 1,6-hexanediol, 97.5 g of 1,4-butanediol, 468.5 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate is used.
  • a composition (PCP-7B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B.
  • Example 8B A mixed solution obtained by mixing 35.8 g of trimethylolpropane, 374.7 g of 1,6-hexanediol, 31.7 g of 1,4-butanediol, 453.0 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was prepared.
  • a composition (PCP-8B) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1B except that it was used.
  • Example 1B Example 1B except that a mixed solution obtained by mixing 196 g of 1,6-hexanediol, 172.8 g of 1,5-pentanediol, 431.2 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was used. In the same manner as above, a composition containing polycarbonate diol (PCD-1B) was obtained.
  • PCD-1B polycarbonate diol
  • Comparative Example 2B 450 g of the composition (PCD-1B) obtained in Comparative Example 1B and 450 g of trimethylolpropane were mixed at 80 ° C. to obtain a composition containing a polycarbonate diol (PCD-2B).
  • a signal of 3.430 ppm or more and 3.530 ppm or less is a signal (S1)
  • a signal of 3.720 ppm or more and 3.800 ppm or less is a signal (S2), and 0.700 ppm or more and 1.130 ppm or less.
  • the signal is the signal (S3) when R 1 of the group represented by the formula (I) is a methyl group (when the polyhydric alcohol (B) is trimethylolethane), and is 0.700 ppm or more and 1.000 ppm.
  • the following signal was taken as the signal (S3) when R 1 of the group represented by the formula (I) was an ethyl group (when the polyhydric alcohol (B) was trimethylolpropane).
  • the results are shown in Tables 6 and 7.
  • 1 H-NMR spectra of the composition obtained in Example 1B are shown in FIGS. 4 to 6.
  • the presence of the compound (A-1) was suggested by the presence of the signal (S1) in PCP-1B to 9B.
  • no signal (S1) was confirmed in PCD-1B to 2B.
  • PCP-1B to 9B the presence of the compound (A-2) was suggested by the presence of the signal (S4) of 3.550 ppm or more and 3.620 ppm or less. Further, in PCP-1B to 6B and PCP - 8B to 9B, the value obtained by subtracting CA1, CA2 and CB from CT from the integral value of the signals (S1) to (S4) may be positive. The confirmation suggests the presence of compound (A-3).
  • composition (unit: g) of Examples 1B to 4B and 6B to 8B and Comparative Example 1B indicates a reaction raw material, and "Example 5B, Reference Example 1B and Comparative Example 2B". "Composition” (unit: g) indicates a compounding ingredient.
  • ⁇ 1,6-hexanediol manufactured by BASF-JAPAN ⁇ 1,9-nonandiol : Kurare, Trimethylol Propane: Sigma-Aldrich, Trimethylol Etan: Fujifilm Wako Pure Chemical Industries, Pentaerythritol: Fujifilm Wako Pure Chemical Industries, Lithium Hydroxide: Tokyo Kasei Kogyo Co., Ltd., Tetrabutyl Titanate: manufactured by Tokyo Kasei Kogyo Co., Ltd. ⁇ Diethyl carbonate: manufactured by Sigma-Aldrich ⁇ Dimethyl carbonate: manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • Lithium acetylacetonate manufactured by Sigma-Aldrich ⁇ JP-508: trade name, 2-ethylhexyl acid Phosphate, manufactured by Johoku Chemical Industries, Ltd.
  • Example 1C 36.1 g of trimethylolpropane, 288 g of 1,6-hexanediol, and 3-methyl-1,5-pentanediol were added to a 1 L double-ended glass reactor with a stirrer, thermometer, heater, and cooler. 123.4 g, 452.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate were charged and mixed. The obtained mixed solution was heated at 130 to 150 ° C. (initial 130 ° C., final stage 150 ° C.) under normal pressure, and reacted for 8 hours while removing low boiling point components (alcohol derived from carbonic acid ester, etc.).
  • the distillate temperature was 77 ° C. or higher and lower than 79 ° C. Further, the pressure in the flask was reduced to 1 kPa at a reaction temperature of 150 ° C., and the reaction was further carried out for 8 hours to obtain a composition (PCP-1C) containing a polycarbonate polyol represented by the above formula (A-1). rice field.
  • PCP-1C a polycarbonate polyol represented by the above formula (A-1). rice field.
  • Example 2C 36.2 g of trimethylolpropane, 205.7 g of 1,6-hexanediol, 205.7 g of 3-methyl-1,5-pentanediol, 452.3 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-2C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except that the mixed solution obtained by charging and mixing was used.
  • Example 3C A mixed solution obtained by charging 36.2 g of trimethylolpropane, 411.5 g of 3-methyl-1,5-pentanediol, 452.3 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate was used.
  • a composition (PCP-3C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C.
  • Example 4C 74.3 g of trimethylolpropane, 353.9 g of 1,6-hexanediol, 39.3 g of 3-methyl-1,5-pentanediol, 432.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-4C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except that the mixed solution obtained by charging and mixing was used.
  • Example 5C Examples except that a mixed solution obtained by charging 60.4 g of trimethylolpropane, 865.4 g of ND-15, 701.7 g of diethyl carbonate, and 0.06 g of lithium acetylacetonate and mixing them was used. In the same manner as in 1C, a composition (PCP-5C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained.
  • Example 6C 900 g of the composition (PCP-1C) obtained in Example 1C and 100 g of trimethylolpropane are mixed at 80 ° C., and a composition containing a polycarbonate polyol represented by the above formula (A-1) (A-1). PCP-6C) was obtained.
  • Example 7C 32.2 g of trimethylolethane, 289.3 g of 1,6-hexanediol, 124.0 g of 3-methyl-1,5-pentanediol, 454.5 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-7C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except that the mixed solution obtained by charging and mixing was used.
  • Example 8C 36.6 g of pentaerythritol, 287.8 g of 1,6-hexanediol, 123.4 g of 3-methyl-1,5-pentanediol, 452.1 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-8C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except that the mixed solution obtained by mixing in the above formula (A-1) was used.
  • Example 9C 36.1 g of trimethylolpropane, 370.3 g of 1,6-hexanediol, 41.1 g of 3-methyl-1,5-pentanediol, 452.4 g of diethyl carbonate, and 0.045 g of lithium acetylacetonate.
  • a composition (PCP-9C) containing a polycarbonate polyol represented by the above formula (A-1) was obtained in the same manner as in Example 1C except that the mixed solution obtained by charging and mixing was used.
  • composition unit: g of Examples 1C to 5C and 7C to 9C indicates the reaction raw material
  • composition unit: g of Examples 6C and Reference Example 1C refers to the compounding component. show.
  • Pentaerythritol Fuji Film Wako Pure Chemical Industries, Ltd.
  • Lithium hydroxide Tokyo Kasei Kogyo Co., Ltd.
  • Tetrabutyl titanate Tokyo Kasei Kogyo Co., Ltd.
  • Nart Sigma-Aldrich
  • JP-508 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industries, Ltd.
  • DOTDL Dioctyltin dilaurate, manufactured by Kishida Chemical Industries, Ltd.
  • Methyl ethyl ketone manufactured by Maruzen Petrochemical Co., Ltd.
  • Toluene manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

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WO2024202836A1 (ja) * 2023-03-31 2024-10-03 東ソー株式会社 組成物及びその製造方法、ウレタン樹脂、水性ウレタン樹脂分散体並びにコーティング剤
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JP2024003928A (ja) 2022-06-28 2024-01-16 ソニーグループ株式会社 画像処理装置、画像処理方法、及び記録媒体
JP7398581B1 (ja) * 2023-02-14 2023-12-14 東ソー株式会社 ポリカーボネートジオール、ウレタン樹脂およびコーティング剤
JP7630777B1 (ja) * 2023-12-04 2025-02-18 東ソー株式会社 ポリカーボネートジオール、ウレタン樹脂およびコーティング剤

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JP2023157780A (ja) * 2022-04-15 2023-10-26 東ソー株式会社 （ポリ）カーボネートポリオール及びその製造方法、組成物及びその製造方法、ウレタン樹脂、水性ウレタン樹脂分散体、並びに、コーティング剤
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JP7601290B1 (ja) * 2023-03-31 2024-12-17 東ソー株式会社 組成物及びその製造方法、ウレタン樹脂、水性ウレタン樹脂分散体並びにコーティング剤
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WO2025088891A1 (ja) * 2023-10-24 2025-05-01 東ソー株式会社 ポリウレタン樹脂形成性組成物、塗装剤セット、塗膜及び塗膜の形成方法
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