WO2024202836A1 - 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 - Google Patents

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 Download PDF

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WO2024202836A1
WO2024202836A1 PCT/JP2024/007151 JP2024007151W WO2024202836A1 WO 2024202836 A1 WO2024202836 A1 WO 2024202836A1 JP 2024007151 W JP2024007151 W JP 2024007151W WO 2024202836 A1 WO2024202836 A1 WO 2024202836A1
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compound
composition
formula
group
represented
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English (en)
French (fr)
Japanese (ja)
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康平 本田
育海 野口
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Tosoh Corp
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Tosoh Corp
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Priority to EP24778977.9A priority Critical patent/EP4674889A1/en
Priority to CN202480022994.9A priority patent/CN121002091A/zh
Priority to KR1020257034304A priority patent/KR20250159254A/ko
Priority to JP2024534414A priority patent/JP7601290B1/ja
Publication of WO2024202836A1 publication Critical patent/WO2024202836A1/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
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—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
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    • 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
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
    • C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
    • C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
    • C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
    • C08G18/8016—Masked aliphatic or cycloaliphatic polyisocyanates
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/64—Polyesters containing both carboxylic ester groups and carbonate 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • 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
    • C08G64/02—Aliphatic polycarbonates
    • C08G64/0208—Aliphatic polycarbonates saturated
    • C08G64/0216—Aliphatic polycarbonates saturated containing a chain-terminating or -crosslinking agent
    • 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
    • C08G64/302—General preparatory processes using carbonates and cyclic ethers
    • 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
    • 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

  • Polycarbonate polyols like polyester polyols and polyether polyols, are useful as raw materials for producing urethane resins (also called polyurethane resins) by reacting them with polyisocyanate compounds, and are useful as raw materials for adhesives, paints, etc.
  • urethane resins also called polyurethane resins
  • polyester polyols have ester bonds
  • urethane resins obtained from polyester polyols have the disadvantage of being poor in hydrolysis resistance.
  • polyether polyols have ether bonds
  • urethane resins obtained from polyether polyols have the disadvantage of being poor in weather resistance and heat resistance.
  • urethane resins obtained from polycarbonate polyols tend to have excellent durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).
  • Patent Documents 1 and 2 propose polycarbonate polyols obtained by transesterification of polycarbonate diols with triol compounds and/or tetraol compounds.
  • an object of one aspect of the present disclosure is to provide a composition that contributes to the formation of a urethane resin having high tensile strength and has good handleability, and a method for producing the same.
  • Another object of the present disclosure is to provide a urethane resin having high tensile strength, and an aqueous urethane resin dispersion and a coating agent using the urethane resin.
  • a composition comprising a compound (A-1) including a repeating unit (A) represented by the following formula (A), a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), a structure (C) derived from an oxetane compound represented by the following formula (C), and a terminal hydroxy group, wherein the content of the structure (C) derived from the oxetane compound represented by the following formula (C) contained in the composition is 0.90 to 10.7 mol % based on the total content of the structure (C) derived from the oxetane compound, the structure (D) derived from a diol represented by the following formula (D), and the structure (E) derived from a polyhydric alcohol represented by the following formula (E) contained in the composition.
  • a repeating unit (A) represented by the following formula (A) a repeating unit (A) represented by the following formula (A)
  • R 1 represents an alkanediyl group, *1-O-R a -*2, or *1-R b -C( ⁇ O)-O-R c -*2, R a , R b , and R c each independently represent an alkanediyl group, *1 represents a bonding site with a carbonyl group, and *2 represents a bonding site with an oxygen atom.
  • R2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond.
  • R3 is a hydrogen atom or an alkyl group, and * indicates a bond.
  • R3 may be the same or different from each other.
  • R2 has the same meaning as defined above, and * represents a bond.
  • a composition comprising a compound (A-1) containing a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I), wherein the content of a structure (C) derived from an oxetane compound represented by the following formula (C) is 2.80 to 28 mol % based on the total of the structural unit (I) derived from a polyhydric alcohol represented by the following formula (I) and the structure (C) derived from the oxetane compound.
  • R 1 represents an alkanediyl group, *1-O-R a -*2, or *1-R b -C( ⁇ O)-O-R c -*2, R a , R b , and R c each independently represent an alkanediyl group, *1 represents a bonding site with a carbonyl group, and *2 represents a bonding site with an oxygen atom.
  • R2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond.
  • [In formula (C), R2 has the same meaning as defined above, and * represents a bond.] [3] The composition according to [1], wherein the content of the structure (C) derived from the oxetane compound is 2.80 to 28 mol % based on the total content of the structural unit (I) derived from the polyhydric alcohol and the structure (C) derived from the oxetan
  • R 1 contains *1-O—R a -*2 and an alkanediyl group.
  • [In formula (d), R a has the same meaning as defined above.]
  • [In formula (e), R2 has the same meaning as defined above.]
  • [In formula (f), R2 has the same meaning as defined above.]
  • [10] The composition according to any one of [1] to [9], further comprising a compound (A-2) represented by the following formula (A-2), a compound (A-3) represented by the following formula (A-3), and a compound (A-4) represented by the following formula (A-4): [In formula (A-2), R 1 has the same meaning as defined above, and n 2 represents an integer of 1 or more.
  • a plurality of R 1's may be the same or different.] [In formula (A-3), R 1 and R 2 are the same as defined above, and n 3 represents an integer of 1 or more. A plurality of R 1s may be the same or different.] [In formula (A-4), R 1 and R 2 are the same as defined above, and n 4 is an integer of 1 or more. A plurality of R 2s may be the same or different. When a plurality of R 1s are present, they may be the same or different.] [11] The composition according to any one of [1] to [3], further comprising lithium acetylacetonate.
  • a method for producing the composition according to any one of [1] to [11], comprising the steps of heating a mixed liquid containing a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and a transesterification catalyst to perform a reflux reaction while removing an alcohol derived from the carbonate ester from the reaction system, thereby obtaining the composition.
  • a method for producing the composition according to any one of [1] to [12], comprising a reaction step of obtaining the compound (A-1) by reacting the polycarbonate polyol (B2) with the polyester polyol (C2) in a mixed solution containing the polycarbonate polyol (B2), a polyester polyol (C2), and a transesterification catalyst, wherein at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) contains a group represented by the following formula (I), or the mixed solution further contains a polyhydric alcohol (E2): [In formula (I), R2 has the same meaning as defined above, and * represents a bond.] [14] The production method according to [12] or [13], wherein 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 (B1), the diol (D1), and the carbonate ester in the mixed solution.
  • a composition and a method for producing the same that contribute to the formation of a urethane resin having high tensile strength and has good handleability.
  • FIG. 1 is a diagram showing the 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1B.
  • FIG. 2 is a diagram showing the 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 1C.
  • a numerical range indicated using “ ⁇ ” indicates a range that includes the numerical values before and after " ⁇ " as the minimum and maximum values, respectively.
  • the minimum or maximum value of a numerical range indicated using “ ⁇ ” can be arbitrarily combined with the maximum or minimum value of another numerical range indicated using " ⁇ ".
  • the upper and lower limit values indicated individually can also be arbitrarily combined.
  • composition of the present disclosure contains a compound (A-1) that includes a repeating unit (A) represented by the following formula (A) and a structural unit (I) derived from a polyhydric alcohol represented by the following formula (I).
  • R 1 represents an alkanediyl group, *1-O-R a -*2, or *1-R b -C( ⁇ O)-O-R c -*2, R a , R b , and R c each independently represent an alkanediyl group, *1 represents a bonding site with a carbonyl group, and *2 represents a bonding site with an oxygen atom.
  • R2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group, and * indicates a bond.
  • the composition according to the first aspect is a composition in which the content of structure (C) derived from an oxetane compound represented by the following formula (C) is 2.80 to 28 mol % relative to the total of structural unit (I) derived from a polyhydric alcohol and structure (C) derived from an oxetane compound.
  • R2 has the same meaning as defined above, and * represents a bond.
  • composition according to the second aspect of the present disclosure is a composition in which the content of structure (C) derived from an oxetane compound is 0.90 to 10.7 mol % relative to the total of structure (C) derived from an oxetane compound, structure (D) derived from a diol represented by the following formula (D), and structure (E) derived from a polyhydric alcohol represented by the following formula (E).
  • R3 is a hydrogen atom or an alkyl group, and * indicates a bond. R3 may be the same or different from each other.
  • R2 has the same meaning as defined above, and * represents a bond.
  • the compound (A-1) is a compound containing the repeating unit (A), the structural unit (I) derived from the polyhydric alcohol, the structure (C) derived from the oxetane compound, and a terminal hydroxyl group.
  • the compound (A-1) may contain the repeating unit (A), the structure (C) derived from the oxetane compound, the structure (D) derived from the diol, and the structure (E) derived from the polyhydric alcohol. and a compound containing the structure (E)
  • the alkanediyl group represented by R 1 may be linear or branched. When there are two or more types of alkanediyl groups represented by R 1 , all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.
  • the number of carbon atoms of the alkanediyl group represented by R1 may be, for example, 2 to 10.
  • Specific examples of the alkanediyl group include an ethanediyl group, a 1,2-propanediyl group, a 1,3-propanediyl group, a 1,2-butanediyl group, a 1,3-butanediyl group, a 1,4-butanediyl group, a 1,5-pentanediyl group, a 2,2-dimethyl-1,3-propanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 1,8-octanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,
  • a 1,4-butanediyl group, a 1,5-pentanediyl group, a 1,6-hexanediyl group, a 3-methyl-1,5-pentanediyl group, a 2-ethyl-1,6-hexanediyl group, a 1,9-nonanediyl group, a 2-methyloctane-1,8-diyl group, and the like are preferable.
  • the alkanediyl group represented by R a , R b , and R c may be the same as the alkanediyl group described above.
  • the number of carbon atoms of the alkanediyl group represented by R a , R b , and R c may be, for example, 2 to 10.
  • R a When there are two or more types of alkanediyl groups represented by R a , all of them may be linear alkanediyl groups or branched alkanediyl groups, or a part of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.
  • alkanediyl groups represented by R b When there are two or more types of alkanediyl groups represented by R b , all of them may be linear alkanediyl groups or branched alkanediyl groups, or a part of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.
  • alkanediyl groups represented by Rc all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other part may be branched alkanediyl groups.
  • the polycarbonate polyol contains two or more types of alkanediyl groups as R 1 , R a , R b or R c , all of them may be linear alkanediyl groups or branched alkanediyl groups, or some of them may be linear alkanediyl groups and the other parts may be branched alkanediyl groups.
  • the alkyl group and hydroxyalkyl group represented by R2 may be linear or branched.
  • the number of carbon atoms in the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, 2 to 5, or 3 to 4.
  • Specific examples of the alkyl group and hydroxyalkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group.
  • R2 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 number average molecular weight of compound (A-1) may be, for example, 200 to 6000 g/mol.
  • the number average molecular weight is the number average molecular weight calculated as a bifunctional polyoxypropylene polyol, measured using GPC (Gel Permeation Chromatography).
  • the hydroxyl value of compound (A-1) may be, for example, 30 to 800 mgKOH/g.
  • the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl groups in 1 g of compound (A-1), and is measured in accordance with JIS K1557-1.
  • Compound (A-1) will be described in more detail below, divided into several embodiments (first to fourth embodiments).
  • the compound (A-1) contains only linear alkanediyl groups as R 1. That is, all of the R 1s are linear alkanediyl groups. Since the compound (A-1) contains only linear alkanediyl groups as R 1 , it tends to become a solid at 25° C.
  • the compound (A-1) contains only one type of linear alkanediyl group as R 1. In this case, the tendency of the compound (A-1) to become a solid at 25° C. is increased.
  • the number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 2 to 9, and even more preferably 4 to 8.
  • Preferred examples of linear alkanediyl groups are 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, and 1,9-nonanediyl.
  • the number average molecular weight of the compound (A-1) of the first embodiment is preferably 200 g/mol to 6000 g/mol, and may be 300 g/mol to 5000 g/mol or 500 g/mol to 4000 g/mol.
  • 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 types of alkanediyl groups as R 1. Since the compound (A-1) contains two or more types of alkanediyl groups as R 1 , it tends to become a liquid at 25°C.
  • the ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as R 1 in compound (A-1) is preferably 0.20 or more (e.g., 0.20 to 0.95), more preferably 0.30 or more (e.g., 0.30 to 0.90), and even more preferably 0.40 or more (e.g., 0.40 to 0.70 or 0.50 to 0.60).
  • the number average molecular weight of the compound (A-1) of the second embodiment is preferably 200 g/mol to 6000 g/mol, and may be 300 g/mol to 5000 g/mol or 500 g/mol to 4000 g/mol.
  • 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.
  • the compound (A-1) contains a branched alkanediyl group as R 1. Since the compound (A-1) of the third embodiment contains a branched alkanediyl group as R 1 , it tends to become a liquid at 25°C.
  • the compound (A-1) may contain two or more types of alkanediyl groups as R 1.
  • the two or more types of alkanediyl groups may all be branched alkanediyl groups, but from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having excellent handleability, good elongation and texture, and excellent durability is easily formed, it is preferable that a part of the two or more types of alkanediyl groups is a linear alkanediyl group.
  • the ratio of the number of moles of the branched alkanediyl groups to the total number of moles of the alkanediyl groups contained as R 1 in the compound (A-1) is preferably 0.10 to 1.00, more preferably 0.20 to 0.90, even more preferably 0.30 to 0.70, and even more preferably 0.40 to 0.60.
  • the number of carbon atoms in the branched alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and even more preferably 4 to 8.
  • the number of carbon atoms in the main chain (the straight chain with the largest number of carbon atoms) of the branched alkanediyl group is preferably 2 to 9, more preferably 3 to 8, and even more preferably 4 to 7.
  • Preferred examples of branched alkanediyl groups are 3-methylpentane-1,5-diyl and 2-methyl-1,8-octanediyl groups.
  • the number of carbon atoms in the linear alkanediyl group is preferably 2 to 10, more preferably 3 to 9, and even more preferably 4 to 8.
  • Preferred examples of linear alkanediyl groups are 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl, and 1,9-nonanediyl.
  • the ratio of the number of moles of 1,6-hexanediyl groups to the total number of moles of alkanediyl groups contained as R 1 in compound (A-1) is preferably 0.05 or more (e.g., 0.05 to 1.00), more preferably 0.10 or more (e.g., 0.10 to 0.90), even more preferably 0.20 or more (e.g., 0.20 to 0.80), and particularly preferably 0.30 or more (e.g., 0.30 to 0.70 or 0.40 to 0.60).
  • the number average molecular weight of the compound (A-1) of the third embodiment is preferably 200 g/mol to 6000 g/mol, and may be 300 g/mol to 5000 g/mol or 500 g/mol to 4000 g/mol.
  • 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 property of the compound (A-1) is not particularly limited, and may be a solid at 25° C. or a liquid at 25° C.
  • the property of the compound (A-1) can be changed depending on the type (carbon number, presence or absence of branching, etc.) of the alkanediyl group contained in the compound (A-1) as R 1 , R a , R b , or R c , as well as the hydroxyl value of the compound (A-1).
  • the compound (A-1) when the total number of moles of branched alkanediyl groups in the compound (A-1) relative to the total number of moles of alkanediyl groups contained in the compound (A-1) as R 1 , R a , R b , or R c is 0.2 to 1.0, and when the hydroxyl value of the compound (A-1) is high, the compound (A-1) is likely to be a liquid at 25° C.
  • R 1 contained in the compound (A-1) is an alkanediyl group and *1-O-R a -*2.
  • the ratio of the number of moles of *1-O-R a -*2 contained as R 1 to the total number of moles of alkanediyl groups, *1-O-R a -*2, and *1-R b -C( ⁇ O)-O-R c -*2 contained as R 1 in compound ( A -1) is preferably 0.10 or more (e.g., 0.10 to 0.90), more preferably 0.20 or more (e.g., 0.20 to 0.80), even more preferably 0.30 or more (e.g., 0.30 to 0.70), and particularly preferably 0.40 or more (e.g., 0.40 to 0.60).
  • the number average molecular weight of the compound (A-1) of the fourth embodiment is preferably 200 g/mol to 6000 g/mol, and may be 300 g/mol to 5000 g/mol or 500 g/mol to 4000 g/mol.
  • the hydroxyl value of the compound (A-1) of the fourth 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 in the first to third embodiments may be, for example, a reaction product of a polyhydric alcohol represented by the following formula (b) (hereinafter also referred to as "polyhydric alcohol (B1)”), a diol represented by the following formula (d) (hereinafter also referred to as “diol (D1)”), and a carbonate ester, or a reaction product of a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an oxetane compound represented by the following formula (f) (hereinafter also referred to as "oxetane compound (F1)").
  • R2 is a hydrogen atom, an alkyl group, or a hydroxyalkyl group.
  • R a has the same meaning as defined above.
  • R2 has the same meaning as defined above.
  • polyhydric alcohols (B1) include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. These may be used alone or in combination of two or more.
  • diols (D1) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 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. These may be used alone or in combination of two or more.
  • carbonate esters examples include dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ethylene carbonate, trimethylene carbonate, and 1,2-propylene carbonate. These may be used alone or in combination of two or more. From the standpoint of ease of availability and ease of setting polymerization reaction conditions, 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.
  • Examples of the oxetane compound (F1) include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. These may be used alone or in combination of two or more.
  • the compound (A-1) described in the fourth embodiment may be, for example, a reaction product of polycarbonate polyol (B2) and polyester polyol (C2).
  • the compound (A-1) may be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), and oxetane compound (F2).
  • the compound (A-1) may be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), diol (D2) and/or polyhydric alcohol (E2).
  • the compound (A-1) may be a reaction product of polycarbonate polyol (B2), polyester polyol (C2), oxetane compound (F2), diol (D2) and/or polyhydric alcohol (E2).
  • the polycarbonate polyol (B2) may be any polycarbonate polyol having two or more hydroxyl functional groups, and may be a polycarbonate polyol (B2-1) having two hydroxyl functional groups (i.e., a polycarbonate diol), a polycarbonate polyol (B2-2) having more than two hydroxyl functional groups, or a combination of two or more selected from polycarbonate polyol (B2-1) and polycarbonate polyol (B2-2).
  • polycarbonate polyol (B2-1) is one obtained by reacting a carbonate ester with a diol.
  • the carbonate esters and diols that can be used in the reaction to obtain the polycarbonate polyol (B2-1) include, for example, the same carbonate esters and diols (D1) as those described in the description of the compound (A-1) in the first to third embodiments.
  • polycarbonate polyols (B2-2) examples include those obtained by reacting a carbonate ester, a diol, and a polyhydric alcohol having three or more hydroxyl functional groups.
  • the carbonate ester, diol, and polyhydric alcohol having three or more hydroxyl functional groups that can be used in the reaction to obtain the polycarbonate polyol (B2-2) include the same carbonate ester, diol (D1), and polyhydric alcohol (B1) as those described in the description of the compound (A-1) in the first to third embodiments.
  • the polyester polyol (C2) may be any polyester polyol having 2 or more hydroxyl functional groups, and may be a polyester polyol (C2-1) having 2 hydroxyl functional groups (i.e., a polyester diol), a polyester polyol (C2-2) having more than 2 hydroxyl functional groups, or a combination of two or more selected from polyester polyol (C2-1) and polyester polyol (C2-2).
  • polyester polyol (C2-1) examples include the following polyester polyols ( ⁇ ) to ( ⁇ ) and combinations of any two or more of these.
  • ⁇ ) A polyester polyol (polyester polyol ( ⁇ )) obtained from a diol (C2-1-1) and a dicarboxylic acid and/or anhydride thereof (C2-1-2).
  • ⁇ ) A polyester polyol (polyester polyol ( ⁇ )) obtained by ring-opening addition polymerization of a cyclic ester compound (C2-1-4) such as a lactone using a diol (C2-1-1) as an initiator.
  • the polyester polyol ( ⁇ ) can be said to be a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.
  • the diol (C2-1-1) may be the same as the diol (D1) described in the description of the compound (A-1) in the first to third embodiments.
  • 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, or 2-methyl-1,8-octanediol is preferred.
  • Dicarboxylic acids and/or their anhydrides include, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, tartaric acid, and their anhydrides, as well as combinations of any two or more of these.
  • Examples of the cyclic ester compound (C2-1-4) include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, 4-methylcaprolactone, ⁇ -caprylolactone, ⁇ -caprylolactone, ⁇ -palmitolactone, and the like, as well as combinations of any two or more of these.
  • ring-opening addition polymers of ⁇ -caprolactone using trimethylolpropane as an initiator are preferred from the standpoint of stability during polymerization and economic efficiency.
  • polyester polyol (C2-2) examples include the following polyester polyols ( ⁇ ') to ( ⁇ ') and any combination of two or more of these.
  • ⁇ ' A polyester polyol (polyester polyol ( ⁇ ')) obtained from a diol (C2-2-1), a dicarboxylic acid and/or anhydride thereof (C2-2-2), and a polyhydric alcohol having three or more hydroxyl functional groups (C2-2-3).
  • the polyester polyol ( ⁇ ') can be said to be a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.
  • the diol (C2-2-1) and polyhydric alcohol (C2-2-3) having 3 or more hydroxyl functional groups can be the same as the diol (D1) and polyhydric alcohol (B1) described in the description of the compound (A-1) in the first to third embodiments.
  • Dicarboxylic acids and/or their anhydrides (C2-2-2) and cyclic ester compounds (C2-2-4) include the same as those mentioned in the explanation of dicarboxylic acids and/or their anhydrides (C2-1-2) and cyclic ester compounds (C2-1-4).
  • the polyester polyol (C2) contains polyester polyol ( ⁇ ) and/or polyester polyol ( ⁇ '), since when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance or moist heat resistance is easily formed.
  • the diol (D2) may be, for example, the same as the diol (D1) described in the description of the compound (A-1) in the first to third embodiments.
  • Examples of the polyhydric alcohol (E2) include the same polyhydric alcohol (B1) as described in the description of the compound (A-1) in the first to third embodiments.
  • Examples of the oxetane compound (F2) include the same oxetane compound (F1) as described in the description of the compound (A-1) in the first to third embodiments.
  • composition may further contain a diol represented by the following formula (d) (hereinafter also referred to as "diol (d)").
  • R a has the same meaning as defined above.
  • the diol (d) has the same meaning as described above, and the alkanediyl group contained as R a in the diol (d) may be the same as the alkanediyl group contained as R a in the compound (A-1).
  • the alkanediyl group contained as R a in diol (d) may be the same as the alkanediyl group contained as R a in compound (A-1).
  • the composition may contain two or more types of diols (d) having different alkanediyl groups represented by R a .
  • the combination of groups contained as R a in the multiple compounds corresponding to diol (d) may be the same as the combination of groups contained as R a in the multiple compounds corresponding to compound (A-1).
  • the diol (d) may be, for example, the same as the diol (D1) described in the description of the compound (A-1) in the first to third embodiments.
  • composition may further contain a polyhydric alcohol represented by the following formula (e) (hereinafter also referred to as "polyhydric alcohol (e)").
  • R2 has the same meaning as defined above.
  • the polyhydric alcohol (e) has the same meaning as described above, and the alkyl group and/or hydroxyalkyl group contained as R 2 in the polyhydric alcohol (e) may be the same as the atom or group contained as R 2 in the compound (A-1).
  • the atom or group contained as R 2 in the polyhydric alcohol (e) may be the same as the atom or group contained as R 2 in the compound (A-1).
  • the composition may contain two or more polyhydric alcohols (e) having different alkanediyl groups represented by R 2.
  • the combination of groups contained as R 2 in the multiple compounds corresponding to the polyhydric alcohol (e) may be the same as the combination of groups contained as R 2 in the multiple compounds corresponding to the compound (A-1).
  • Examples of the polyhydric alcohol (e) include the same polyhydric alcohol (B1) as described in the description of the compound (A-1) in the first to third embodiments.
  • composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as “oxetane compound (F)").
  • R2 has the same meaning as defined above.
  • the oxetane compound (F) has the same meaning as described above, and the alkyl group and hydroxyalkyl group contained as R 2 in the oxetane compound (F) may be the same as the atom or group contained as R 2 in the compound (A-1).
  • the atom or group contained as R 2 in the oxetane compound (F) may be the same as the atom or group contained as R 2 in the compound (A-1).
  • the composition may contain two or more types of compounds (A-1) having different alkanediyl groups represented by R 2
  • the composition may contain two or more types of oxetane compounds (F) having different alkanediyl groups represented by R 2.
  • the combination of groups contained as R 2 in the multiple compounds corresponding to the oxetane compound (F) may be the same as the combination of groups contained as R 2 in the multiple compounds corresponding to the compound (A-1).
  • the oxetane compound (F) may be, for example, the same as the oxetane compound (F1) described in the description of the compound (A-1) in the first to third embodiments.
  • composition may further contain a polycarbonate compound represented by the following formula (A-2) (hereinafter referred to as "compound (A-2)").
  • R 1 has the same meaning as defined above, and n 2 represents an integer of 1 or more.
  • a plurality of R 1's may be the same or different.
  • composition may further contain a polycarbonate compound represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)").
  • R 1 and R 2 are the same as defined above, and n 3 represents an integer of 1 or more. When a plurality of R 1s are present, the plurality of R 1s may be the same or different.]
  • composition may further contain a polycarbonate compound represented by the following formula (A-4) (hereinafter referred to as "compound (A-4)").
  • R 1 and R 2 are the same as defined above, and n 4 is an integer of 1 or more.
  • a plurality of R 2 's may be the same or different.
  • the R 1 's may be the same or different.
  • the group contained as R 1 in the compounds (A-2) to (A-4) may be the same as the group contained as R 1 in the compound (A-1).
  • the compounds (A-2) to (A-4) may also contain two or more types of groups as R 1.
  • the combination of two or more types of groups contained as R 1 in the compounds (A-2) to (A-4) may be the same as the combination of two or more types of groups contained as R 1 in the compound (A-1).
  • the group contained as R 2 in the compounds (A-2) to (A-4) may be the same as the group contained as R 2 in the compound (A-1).
  • the compounds (A-2) to (A-4) may also contain two or more groups as R 2.
  • the combination of two or more groups contained as R 2 in the compounds (A-2) to (A-4) may be the same as the combination of two or more groups contained as R 2 in the compound (A-1).
  • n 2 , n 3 , and n 4 may be 1-65, or 2-60, or 3-50.
  • the number average molecular weight of compounds (A-2) to (A-4) is preferably 200 g/mol to 6000 g/mol, and may be 300 g/mol to 5000 g/mol or 500 g/mol to 4000 g/mol.
  • the hydroxyl value of compounds (A-2) to (A-4) is preferably 30 to 800 mgKOH/g, and may be 40 to 700 mgKOH/g or 50 to 600 mgKOH/g.
  • the lower limit of the deemed average hydroxyl functionality of the composition may be, for example, 2.0 or more, 2.1 or more, 2.2 or more, 2.3 or more, 2.4 or more, or 2.5 or more.
  • the upper limit of the deemed average hydroxyl functionality of the composition may be, for example, 3.90 or less, 3.80 or less, 3.70 or less, 3.60 or less, 3.50 or less, or 3.40 or less.
  • the deemed average hydroxyl functionality of the composition may be 2.0 to 3.90, for example, 2.1 to 3.80, 2.2 to 3.70, 2.3 to 3.50, or 2.5 to 3.40.
  • the handling properties and the elongation at break in the tensile test are further improved.
  • the strength at break and the softening temperature in the tensile test tend to be further improved.
  • the sum of the total number of moles of groups represented by the following formula (I) and the total number of moles of groups represented by the following formula (C) contained in the composition is represented by CT
  • the total number of moles of groups represented by the following formula (C) contained in the composition is represented by CC
  • the total number of moles of groups represented by the following formula (D) contained in the composition is represented by CD
  • the total number of moles of groups represented by the following formula (E) contained in the composition is represented by CE .
  • the content (unit: mol%) of the structure (C) derived from an oxetane compound relative to the sum of the structural unit (I) derived from a polyhydric alcohol and the structure (C) derived from an oxetane compound is represented by "molar ratio ( CC / CT x 100)".
  • the content (unit: mol%) of the structure (C) derived from an oxetane compound relative to the sum of the structure (C) derived from an oxetane compound, the structure (D) derived from a diol, and the structure (E) derived from a polyhydric alcohol is represented by "molar ratio ( CC /( CC + CD + CE ) x 100)".
  • R2 has the same meaning as defined above, and * represents a bond.
  • R2 has the same meaning as defined above, and * represents a bond.
  • R3 is a hydrogen atom or an alkyl group, and * indicates a bond. R3 may be the same or different from each other.
  • R2 has the same meaning as defined above, and * represents a bond.
  • the molar ratio (C C /C T ⁇ 100) may be 2.80 to 28.0.
  • the molar ratio (C C /(C C +C D +C E ) ⁇ 100) may be 0.90 to 10.7.
  • the molar ratio (C C /C T ⁇ 100) and the molar ratio (C C /(C C +C D +C E ) ⁇ 100) are each within the above ranges, when the composition is used as a raw material for a urethane resin, a urethane resin that has both good handleability and high tensile strength tends to be formed.
  • the molar ratio (C C /C T ⁇ 100) and the molar ratio (C C /(C C +C D +C E ) ⁇ 100) can be determined, for example, from 1 H-NMR measurement of the composition using deuterated chloroform as a solvent and tetramethylsilane as a reference substance and from the integral value of the signal in the 1 H-NMR spectrum obtained by the measurement.
  • the molar ratio (C C /C T ⁇ 100) can be calculated from the ratio of the integral value ⁇ SI (corresponding to 3 mol of hydrogen atoms) of the signal (SI) of the terminal methyl of R 2 (alkyl group) in formula (I) and formula (C) to the integral value ⁇ SC (corresponding to 4 mol of hydrogen atoms) of the signal (SC) of the methylene located next to the oxygen atom of the oxetane group in formula (C).
  • the molar ratio ( CC /( CC + CD + CE )x100) can be calculated from the ratio of the integral value ⁇ SC (4 mol hydrogen atoms) of the signal (SC), the integral value ⁇ SD (2 mol hydrogen atoms) of the signal (SD) of the methylene located next to the hydroxyl group in the group represented by formula (D), and the integral value ⁇ SE (4 mol hydrogen atoms) of the signal (SE) of the methylene located next to the hydroxyl group in the group represented by formula (E).
  • the molar ratio ( CC / CTx100 ) can be rephrased as 0.75 times the ratio of the integral value ⁇ SI of the signal (SI) to the integral value ⁇ Sf of the signal (Sf) ( 0.75x ⁇ Sf / ⁇ SIx100 ).
  • the molar ratio ( CC /( CC + CD + CE ) ⁇ 100) can be expressed in other words as ( ⁇ SC /( ⁇ SC +2 ⁇ SD+ ⁇ SE) ⁇ 100), which is the ratio of the integral value ⁇ SC of the signal (SC), the integral value ⁇ SD of the signal ( SD ) , and the integral value ⁇ SE of the signal ( SE ), to the integral value ⁇ SC of the signal ( SC ).
  • the signal (SC) is observed in the range of 4.390 ppm to 4.500 ppm in the 1 H-NMR spectrum
  • the signal (SD) is observed in the range of 3.618 ppm to 3.720 ppm in the 1 H-NMR spectrum
  • the signal (SE) is observed in the range of 3.590 ppm to 3.618 ppm in the 1 H-NMR spectrum.
  • the above signal (SI) is observed in the range of 0.700 ppm or more and 1.000 ppm or less
  • R 2 in formula (I) and formula (C) is a methyl group
  • the above signal (SI) is observed in the range of 0.700 ppm or more and 1.130 ppm or less. Therefore, in the first and second embodiments, the molar ratio (C C /C T ⁇ 100) and the molar ratio (C C /(C C +C D +C E ) ⁇ 100) can be calculated from the ratio of the integral values of these signals.
  • the signal (SC) when 1 H-NMR measurement of the composition is performed using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, for example, the signal (SC) is observed in the range of 4.390 ppm to 4.500 ppm in the 1 H-NMR spectrum, the signal (SD) is observed in the range of 3.618 ppm to 3.720 ppm in the 1 H-NMR spectrum, and the signal (SE) is observed in the range of 3.590 ppm to 3.618 ppm in the 1 H-NMR spectrum. Therefore, in the third embodiment, the molar ratio (C C /(C C +C D +C E ) ⁇ 100) can be calculated from the ratio of the integral values of these signals.
  • the signal (SC) is observed in the range of 4.390 ppm to 4.500 ppm in the 1 H-NMR spectrum
  • the signal (SD) is observed in the range of 3.618 ppm to 3.720 ppm in the 1 H-NMR spectrum
  • the signal (SE) is observed in the range of 3.550 ppm to 3.618 ppm in the 1 H-NMR spectrum.
  • the above signal (SI) is observed in the range of 0.700 ppm to 1.000 ppm
  • R2 in formula (I) and formula (C) is a methyl group
  • the above signal (SI) is observed in the range of 0.700 ppm to 1.130 ppm. Therefore, in the fourth embodiment, the molar ratio ( C / Cx x 100) and the molar ratio ( C /( C+C + C ) x 100) can be calculated from the ratio of the integral values of these signals.
  • the molar ratio (C C /C T ⁇ 100) in the composition of the first to second embodiments and the fourth embodiment may be 2.80 or more, 3.00 or more, 3.20 or more, 3.40 or more, 3.60 or more, 3.80 or more, 5.00 or more, 6.00 or more, 7.00 or more, 8.00 or more, 9.00 or more, or 10.0 or more.
  • a polyurethane resin having excellent handleability tends to be formed.
  • the molar ratio (C C /C T ⁇ 100) may be 28.0 or less, 26.0 or less, 22.0 or less, 20.0 or less, 18.0 or less, 16.0 or less, 15.0 or less, 14.0 or less, 13.0 or less, or 12.0 or less.
  • a polyurethane resin having excellent tensile strength tends to be formed.
  • the molar ratio (C C /C T ⁇ 100) may be 2.0 to 30.0, 3.0 to 28.0, 3.2 to 26.0, 3.4 to 22.0, 3.8 to 20.0, 5.0 to 18.0, 6.0 to 16.0, 7.0 to 15.0, 8.0 to 14.0, 9.0 to 13.0, or 10.0 to 12.0.
  • a polyurethane resin having both good handling properties and tensile strength tends to be formed.
  • the molar ratio ( CC /( CC + CD + CE ) ⁇ 100) in the compositions of the first to fourth embodiments may be 0.90 or more, 0.95 or more, 1.00 or more, 1.05 or more, 1.10 or more, 1.15 or more, 1.20 or more, 1.50 or more, 1.80 or more, 2.10 or more, 2.40 or more, 3.00 or more, or 4.00 or more.
  • a polyurethane resin having excellent handleability tends to be formed.
  • the molar ratio ( CC /( CC + CD + CE )x100) may be 16.0 or less, 10.7 or less, 10.5 or less, 10.0 or less, 9.5 or less, 9.0 or less, 8.5 or less, 8.0 or less, 7.5 or less, 7.0 or less, 6.5 or less, or 6.0 or less.
  • a polyurethane resin having particularly excellent tensile strength tends to be formed.
  • the molar ratio ( CC /( CC + CD + CE ) ⁇ 100) may be 1.00 to 10.7, 1.05 to 10.5, 1.10 to 10.0, 1.15 to 9.5, 1.20 to 9.0, 1.30 to 8.0, 1.50 to 7.0, or 1.80 to 6.0.
  • the molar ratio ( CC /( CC + CD + CE ) ⁇ 100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin having both good handleability and tensile strength tends to be formed.
  • compositions of the first to third embodiments may be a reaction mixture of a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an oxetane compound (F1) added as needed.
  • 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 composition of the fourth embodiment may be a reaction mixture of polycarbonate polyol (B2), polyester polyol (C2), and diol (d), polyhydric alcohol (e), and/or oxetane compound (F2) added as necessary.
  • the above reaction is usually carried out in the presence of a transesterification catalyst, so 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 mass% based on the total mass of the composition.
  • the properties of the composition are not particularly limited, and may be a solid at 25°C or a liquid at 25°C.
  • the properties of the composition can be changed depending on the types and content ratios of the components contained (e.g., compounds (A-1) to (A-4), diol (d), polyhydric alcohol (e), and oxetane compound (F)).
  • the number average molecular weight of the composition may be, for example, 200 to 6000 g/mol.
  • the lower limit of the number average molecular weight of the composition may be, for example, 200 g/mol or more, 400 g/mol or more, 600 g/mol or more, 800 g/mol or more, 1000 g/mol or more, 1200 g/mol or more, 1400 g/mol or more, 1600 g/mol or more, or 1800 g/mol or more.
  • the upper limit of the number average molecular weight of the composition may be, for example, 6000 g/mol or less, 5000 g/mol or less, 4000 g/mol or less, 3000 g/mol or less, 2500 g/mol or less, 2000 g/mol or less, 1800 g/mol or less, 1600 g/mol or less, 1400 g/mol or less, 1200 g/mol or less, 1000 g/mol or less, or 800 g/mol or less.
  • the number average molecular weight of the composition is the number average molecular weight calculated as a bifunctional polyoxypropylene polyol, measured using GPC (Gel Permeation Chromatography) with the entire composition as the measurement subject.
  • the hydroxyl value of the composition may be, for example, 30 to 800 mgKOH/g.
  • the lower limit of the hydroxyl value of the composition may be, for example, 30 mgKOH/g or more, 40 mgKOH/g or more, 50 mgKOH/g or more, 60 mgKOH/g or more, 70 mgKOH/g or more, 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more, 120 mgKOH/g or more, 140 mgKOH/g or more, 160 mgKOH/g or more, or 180 mgKOH/g or more.
  • the upper limit of the hydroxyl value of the composition may be, for example, 800 mgKOH/g or less, 700 mgKOH/g or less, 600 mgKOH/g or less, 500 mgKOH/g or less, 400 mgKOH/g or less, 300 mgKOH/g or less, 250 mgKOH/g or less, 200 mgKOH/g or less, 180 mgKOH/g or less, 160 mgKOH/g or less, 140 mgKOH/g or less, 120 mgKOH/g or less, 100 mgKOH/g or less, or 80 mgKOH/g or less.
  • This embodiment can provide a composition that contributes to the formation of a urethane resin with high tensile strength and has good handling properties.
  • a mixed liquid containing a polyhydric alcohol (B1), a diol (D1), a carbonate ester, and an ester exchange catalyst may be heated to perform a reflux reaction (ester exchange reaction) while removing an alcohol derived from the carbonate ester from the reaction system, thereby obtaining compound (A-1); or a mixed liquid containing a polyhydric alcohol (B1), a diol (D1), a carbonate ester, an oxetane compound (F1), and an ester exchange catalyst may be heated to perform a reflux reaction (ester exchange reaction) while removing an alcohol derived from the carbonate ester from the reaction system, thereby obtaining compound (A-1).
  • the composition of the above embodiment can also be obtained as a reaction mixture containing compound (A-1). Therefore, the above method can also be said to be a method for producing the composition of the above embodiment.
  • the details of the polyhydric alcohol (B1), diol (D1), carbonate ester, and oxetane compound (F1) are as described above, and suitable examples thereof (preferred examples of R 1 and R 2 , and preferred combination examples) are the same as the preferred examples and preferred combination examples of R 1 and R 2 in compound (A-1).
  • As the transesterification catalyst it is preferable to use lithium acetylacetonate, from the viewpoint of facilitating the production of the desired compound (A-1).
  • the ratio of the number of moles of 1,6-hexanediol to the total number of moles of diol (D1) is preferably 0.20 or more (e.g., 0.20 to 1.00), more preferably 0.30 or more (e.g., 0.30 to 0.90), and even more preferably 0.40 or more (e.g., 0.40 to 0.80 or 0.50 to 0.70).
  • the mixing ratio of the polyhydric alcohol (B1) and the diol (D1) is preferably 1/100 to 5/1, more preferably 1/80 to 3/1, even more preferably 1/50 to 2/1, and particularly preferably 1/20 to 1/1, in molar ratio.
  • the above mixing ratio may be 1/5 to 60/1 or 1/1 to 40/1, in molar ratio.
  • the mixing ratio of the carbonate ester to the polyhydric alcohol (B1) and the diol (D1) is preferably 1/3 to 3/1, more preferably 1/2.5 to 2.5/1, even more preferably 1/2 to 2/1, and particularly preferably 1/1.5 to 1.5/1, in molar ratio.
  • the content of the transesterification catalyst in the mixed solution of the first to third embodiments may be 0.0001 to 0.1 parts by mass, or may be 0.0005 to 0.01 parts by mass, per 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed solution, from the viewpoint of easily controlling the reaction temperature and suppressing an increase in the color number of the reaction product.
  • the content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more, per 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed solution.
  • the content of the transesterification catalyst in the mixed liquid is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed liquid.
  • the content of the transesterification catalyst in the mixed liquid is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyhydric alcohol, diol, and carbonate ester in the mixed liquid.
  • the heating temperature (reaction temperature) of the mixed liquid of the first to third embodiments may be, for example, 80 to 250 ° C., or 100 to 220 ° C.
  • reaction temperature 80 ° C. or higher
  • the transesterification reaction easily proceeds, and the desired compound (A-1) is easily obtained.
  • reaction temperature 250 ° C. or lower
  • the number of colors of the obtained compound (A-1) and the composition polyol is suppressed.
  • the transesterification reaction may be performed while keeping the temperature constant, or may be performed while increasing the temperature stepwise or continuously depending on the reaction progress.
  • the degree of reaction progress can be estimated from the amount of distillate. 120°C ⁇ T1 ⁇ 155°C...( ⁇ ) 140°C ⁇ T2 ⁇ 155°C...( ⁇ ) T1 ⁇ T2...( ⁇ ) T1 m ⁇ T2 m ...( ⁇ )
  • the heating of the mixture in the first to third embodiments can be carried out under normal pressure, but in the latter half of the reaction, it can also be carried out under reduced pressure (for example, under a pressure of 101 to 0.1 kPa). This makes it possible to increase the distillation rate of the distillate produced and speed up the progress of the reaction.
  • normal pressure means a pressure of 101.325 kPa ⁇ 20.000 kPa.
  • the heating of the mixture preferably includes heating under a pressure of 101.325 kPa ⁇ 20.000 kPa (first heating) and then heating under a reduced pressure of 10.000 kPa or less (second heating), and it is more preferable that the temperature of the first heating is a temperature T1 that satisfies the relationship of the above formula ( ⁇ ), and the temperature of the second heating is a temperature T2 that satisfies the relationship of the above formula ( ⁇ ), and it is even more preferable that the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of the above formula ( ⁇ ). Furthermore, from the viewpoint of facilitating the production of the compound (A-1), it is preferable to remove the alcohol derived from the carbonate ester from the reaction system by distilling it at 120° C. or less.
  • the reaction time of the mixed solution of the first to third embodiments may be 2 to 80 hours, 3 to 60 hours, 4 to 50 hours, 5 to 40 hours, or 6 to 30 hours.
  • the structure (C) derived from the oxetane compound represented by the above formula (C) is generated by an intramolecular dehydration reaction of a polyhydric alcohol and/or an intramolecular decarboxylation reaction of a cyclic carbonate, which is a reaction product of a polyhydric alcohol and a carbonate ester.
  • the above intramolecular dehydration reaction and intramolecular decarboxylation reaction are irreversible reactions, and the amount of the structure (C) derived from the oxetane compound generated increases with reaction time.
  • reaction time When the reaction time is 2 hours or more, it is possible to promote the generation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition in which the molar ratio (C C /C T ⁇ 100) and/or the molar ratio (C C /(C C +C D +C E ) ⁇ 100) satisfies the above-mentioned numerical range. Furthermore, when the reaction time is less than 80 hours, it is possible to suppress the formation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition containing the desired compound (A-1).
  • the compound (A-1) of the fourth embodiment can be obtained, for example, by a method including a reaction step of obtaining compound (A-1) by reacting (ester exchange reaction) polycarbonate polyol (B2) with polyester polyol (C2) in a mixed liquid containing polycarbonate polyol (B2), polyester polyol (C2), and an ester exchange catalyst.
  • at least one of polycarbonate polyol (B2) and polyester polyol (C2) may contain a group represented by the above formula (I), or the mixed liquid may further contain a polyhydric alcohol represented by the above formula (e).
  • the mixed liquid may further contain an oxetane compound (F2).
  • the compound (A-1) of the fourth embodiment can also be obtained by a method including a reaction step in which the compound (A-1) is obtained by reacting (transesterification) the polycarbonate polyol with the polyester polyol in a mixed liquid containing the polycarbonate polyol (B2), the polyester polyol (C2), the transesterification catalyst, and the oxetane compound (F2).
  • the composition of the above embodiment can also be obtained as a reaction mixture containing compound (A-1). Therefore, the above method can also be said to be a method for producing the composition of the above embodiment.
  • the mixed solution of the fourth embodiment may contain a diol (D2) and/or an oxetane compound (F2) as an optional component. Even if the above method is a method in which at least one of the polycarbonate polyol (B2) and the polyester polyol (C2) contains a group represented by the above formula (I), the mixed solution may contain a polyhydric alcohol (E2) as an optional component.
  • the details of the polycarbonate polyol (B2), the polyester polyol (C2), the diol (D2), the polyhydric alcohol (E2) and the oxetane compound (F2) are as described above, and the preferred examples thereof (preferred examples of R 1 and R 2 , and preferred combination examples) are the same as the preferred examples and preferred combination examples of R 1 and R 2 possessed by the compound (A-1).
  • the transesterification catalyst it is preferable to use lithium acetylacetonate from the viewpoint of making it easier to obtain the desired compound (A-1).
  • the mixing ratio of polycarbonate polyol (B2) to polyester polyol (C2) is preferably 95/5 to 5/95 by weight, more preferably 90/10 to 10/90, even more preferably 80/20 to 20/80, and particularly preferably 70/30 to 30/70.
  • the mixing ratio of the polycarbonate polyol (B2) to the polyester polyol ( ⁇ ) and/or polyester polyol ( ⁇ ') is preferably 95/5 to 5/95 by weight, more preferably 90/10 to 10/90, even more preferably 80/20 to 20/80, and particularly preferably 70/30 to 30/70.
  • the content of the transesterification catalyst in the mixed solution of the fourth embodiment may be 0.0001 to 0.1 parts by mass, 0.001 to 0.050 parts by mass, or 0.005 to 0.01 parts by mass relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the reaction temperature and suppressing an increase in the color number of the reaction product.
  • the content of the transesterification catalyst in the mixed solution is preferably 0.001 parts by mass or more, more preferably 0.002 parts by mass or more, and even more preferably 0.003 parts by mass or more relative to 100 parts by mass of the total amount of the polyol components in the mixed solution, from the viewpoint of easily controlling the urethanization reaction.
  • the content of the transesterification catalyst in the mixed solution is preferably 0.050 parts by mass or less, more preferably 0.040 parts by mass or less, and even more preferably 0.030 parts by mass or less, relative to 100 parts by mass of the total amount of the polyol components in the mixed solution.
  • the content of the transesterification catalyst in the mixed solution is preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.040 parts by mass, and even more preferably 0.003 to 0.030 parts by mass, relative to 100 parts by mass of the total amount of the polyol components in the mixed solution.
  • the total amount of the polyol components is the total amount of the compounds having two or more hydroxyl groups (for example, polycarbonate polyol (B2), polyester polyol (C2), polyhydric alcohol (E2), and optional diol (D2)) and the oxetane compound (F2) contained in the mixed solution.
  • the reaction may be progressed by heating the mixed liquid, or may be progressed without heating.
  • the reaction temperature of the mixed liquid is, for example, 0 to 250 ° C., and may be 100 to 220 ° C.
  • the reaction temperature is 0 ° C. or higher, the transesterification reaction is likely to proceed, and the desired compound (A-1) is likely to be obtained.
  • the reaction temperature is 0 ° C. or higher, the generation of structure (C) derived from oxetane derived from polyhydric alcohol having three or more functional groups, which is a by-product of decarboxylation reaction of carbonate groups or dehydration reaction between terminal hydroxyl groups, can be promoted.
  • the reaction temperature is 250 ° C. or lower, the number of colors of the obtained compound (A-1) and composition (polyol-containing composition) is suppressed. Furthermore, when the reaction temperature is 250 ° C. or lower, the generation of structure (C) derived from oxetane derived from polyhydric alcohol having three or more functional groups, which is a by-product of decarboxylation reaction of carbonate groups or dehydration reaction between terminal hydroxyl groups, can be suppressed.
  • the transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while increasing the temperature stepwise or continuously depending on the degree of reaction progress.
  • the degree of reaction progress can be estimated from the consumption amount of the raw material obtained from the GPC chart. 180°C ⁇ T1 ⁇ 200°C...( ⁇ ') 190°C ⁇ T2 ⁇ 200°C...( ⁇ ') T1 ⁇ T2...( ⁇ ') T1 m ⁇ T2 m ...( ⁇ ')
  • the heating of the mixed liquid in the fourth embodiment can be carried out under normal pressure, but can also be carried out under reduced pressure (for example, under a pressure of 101 to 1 kPa). This makes it possible to remove any moisture remaining in the mixed liquid, speed up the reaction, and suppress discoloration of the composition.
  • normal pressure means a pressure of 101.325 kPa ⁇ 20.000 kPa.
  • the heating of the mixture preferably includes heating under a pressure of 101.325 kPa ⁇ 20.000 kPa (first heating) and then heating under a reduced pressure of 20.000 kPa or less (second heating), and it is more preferable that the temperature of the first heating is temperature T1 that satisfies the relationship of formula ( ⁇ ') above, and the temperature of the second heating is temperature T2 that satisfies the relationship of formula ( ⁇ ') above, and it is even more preferable that the temperature of the first heating (temperature T1) and the temperature of the second heating (temperature T2) satisfy the relationship of formula ( ⁇ ') above.
  • the reaction time of the mixed solution of the fourth embodiment may be 1 to 40 hours, 2 to 30 hours, 3 to 20 hours, 4 to 15 hours, or 5 to 12 hours.
  • the structure (C) derived from the oxetane compound represented by the above formula (C) is generated by an intramolecular dehydration reaction of a polyhydric alcohol and/or an intramolecular decarboxylation reaction of a cyclic carbonate, which is a reaction product of a polyhydric alcohol and a carbonate ester.
  • the above intramolecular dehydration reaction and intramolecular decarboxylation reaction are irreversible reactions, and the amount of the structure (C) derived from the oxetane compound generated increases with reaction time.
  • reaction time When the reaction time is 2 hours or more, it is possible to promote the generation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition in which the molar ratio (C C /C T ⁇ 100) and/or the molar ratio (C C /(C C +C D +C E ) ⁇ 100) satisfies the above-mentioned numerical range. Furthermore, when the reaction time is less than 80 hours, it is possible to suppress the formation of the structure (C) derived from the oxetane compound, and it is easy to obtain a composition containing the desired compound (A-1).
  • the mixed solution in the fourth embodiment can also be heated while flowing in nitrogen. This makes it possible to remove moisture from the mixed solution and speed up the progress of the reaction. Furthermore, purging with nitrogen makes it possible to suppress discoloration of the composition. From the viewpoint of making it easier to obtain the desired compound (A-1), the nitrogen flow rate of the mixed solution is preferably 2 to 1000 ml/min/scale (kg), and more preferably 5 to 200 ml/min/scale (kg).
  • the obtained reaction mixture may be subjected to post-treatment such as distillation and drying.
  • post-treatment such as distillation and drying.
  • components such as compound (A-2) to compound (A-4), diol (d), polyhydric alcohol (e), and oxetane compound (F) may be added to prepare the compound.
  • the urethane resin is a polycondensation product of a polyol component and a polyisocyanate component, or a crosslinked product thereof.
  • the crosslinked product means a product in which polycondensation products are crosslinked with each other by a chain extender or the like.
  • the polyol component includes the compound (A-1).
  • the polyol component may include a polyol (a compound having two or more terminal hydroxyl groups) other than the compound (A-1), or a monool (a compound having one terminal hydroxyl group).
  • the polyol component may further include, for example, a polyol (compound (A-2), compound (A-3), compound (A-4), diol (d), polyhydric alcohol (e), oxetane compound (F), etc.) that may be included in the composition.
  • the content ratio of these polyols may be the same as the content ratio of the polyol in the composition (for example, molar ratio (C C /C T ⁇ 100), molar ratio (C C / (C C +C D +C E ) ⁇ 100)).
  • the polyol component may include a polyol mixture obtained by excluding compounds other than the polyol from the composition.
  • the polyol component may further contain a polyol having an acidic group.
  • the urethane resin contains an acidic group.
  • the urethane resin having an acidic group is preferably used in 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) that can impart hydrophilicity to the isocyanate-terminated prepolymer obtained by reaction with an isocyanate.
  • a functional group hydrophilic group
  • polyols having such acidic groups include dimethylolalkanoic acids such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), dimethylolpentanoic acid, and dimethylolnonanoic acid.
  • polyisocyanate examples include aromatic polyisocyanates, aromatic aliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Modified polyisocyanates that are modified versions of these can also be used. Examples of modified polyisocyanates include isocyanurate-modified polyisocyanates (isocyanate trimers), allophanate-modified polyisocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, biuret-modified polyisocyanates, uretonimine-modified polyisocyanates, and acylurea-modified polyisocyanates. These can be used alone or in combination of two or more.
  • Aromatic isocyanates include, for example, 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 ether These include phenyl diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropan
  • Aromatic aliphatic isocyanates include, for example, 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, etc.
  • Aliphatic isocyanates include, for example, hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2'-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4, Examples include 4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-di
  • alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanato-n-butylidene)pentaerythritol, and hydrogenated dimer acid diisocyanate.
  • the blending ratio of the polyol component to the polyisocyanate component is preferably from 9:1 to 1:9, and more preferably from 6:4 to 4:6. When the blending ratio is within this range, the urethane resin tends to have better performance.
  • the chain extender can be appropriately selected depending on the purpose, application, etc.
  • Examples of the chain extender include water, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decanediol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecane dimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis[4-(2-hydroxyethoxy)phenyl]propane, and bis[4-(2-hydroxyethoxy)phenyl]sulfone.
  • high molecular weight polyols such as polyester polyols, polyesteramide polyols, polyether polyols, polyether ester polyols, polycarbonate polyols, and polyolefin polyols
  • polyamines such as ethylene diamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethylethanolamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine, and pentaethylene hexamine can be used.
  • the amount of the chain extender (the proportion of the structure derived from the chain extender contained in the urethane resin) may be 0.1 to 50 parts by mass relative to 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.
  • the chain extender is a polyol
  • the content of the polyol is calculated assuming that the polyol is included in both the chain extender and the polyol component.
  • the urethane resin can be obtained by reacting (urethanization reaction) a polyol component, a polyisocyanate component, and optionally a chain extender.
  • the urethane reaction can be carried out at room temperature (e.g., 25°C) or under heating (e.g., 40 to 200°C).
  • a catalyst can be added for the purpose of shortening the reaction time, improving the reaction rate, etc.
  • catalysts include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and metal catalysts such as tin-based catalysts such as stannous octoate, stannous oleate, and dibutyltin dilaurate. These can be used alone, or two or more types can be used in combination. Of these, dibutyltin dilaurate is preferably used.
  • the amount of catalyst used may be 0.001 to 100 parts by mass per 100 parts by mass of the total amount of the polyol component and the polyisocyanate component.
  • the phosphorus compound is not particularly limited, and examples thereof include phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate; acidic phosphate esters such as methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, acetylene glycol
  • phosphate triesters such as trimethyl phosphate, triethyl phosphate, tributyl
  • phosphite trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris(2-ethylhexyl)phosphite, tridecyl phosphite, trilauryl phosphite, tris(tridecyl)phosphite, trioleyl phosphite, diphenyl mono(2-ethylhexyl)phosphite, diphenyl monodecyl phosphite, diphenyl (monodecyl) phosphite, trilauryl phosphite, diethyl hydrogen phosphite, bis(2-ethylhexyl)phosphite
  • phosphorous esters include bis(decyl)pentaerythritol diphosphite, dilauryl hydrogen phosphite,
  • the amount of the phosphorus compound used may be 10 to 2000 parts by mass relative to 100 parts by mass of the catalyst.
  • the urethanization reaction can be carried out in the presence of a solvent.
  • the solvent that can be used include esters such as ethyl acetate, butyl acetate, propyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; sulfoxides such as dimethylsulfoxide; ethers such as tetrahydrofuran, dioxane, and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and aromatic hydrocarbons such as benzene and toluene.
  • the urethane resin described above has good elongation and texture, excellent durability, and in some cases good breaking strength. Therefore, the urethane resin can be suitably used for synthetic leather, artificial leather, coating agents, etc.
  • the coating agent of the present embodiment contains the above-mentioned urethane resin. Specific aspects of the urethane resin may be as described above.
  • the in-mold painting method that applies RIM involves molding a plastic substrate inside an injection molding die, and then forming a urethane coating on the surface of the molded product inside the die.
  • RIM Reaction Injection Molding
  • the internal volume of the die is constant, and not only are the density, thickness, and hardness of the urethane coating stable, but it is also possible to faithfully reproduce the irregularities on the die surface, resulting in a highly aesthetically pleasing appearance.
  • 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 (a polyol component containing a polyol having an acidic group).
  • aqueous medium in addition to water, a solution containing an emulsifier, a dispersant, etc. can be used.
  • the aqueous medium preferably contains water, and more preferably consists of water only.
  • the acidic groups of the urethane resin may be neutralized with a neutralizing agent.
  • neutralizing agents include organic amines such as ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine, N-methylmorpholine, 2-amino-2-ethyl-1-propanol, and higher alkyl-modified morpholine; alkali metals such as lithium, potassium, and sodium; and inorganic alkalis such as sodium hydroxide and potassium hydroxide.
  • neutralizing agents that dissociate easily when heated, such as ammonia, trimethylamine, and triethylamine, are preferably used. These neutralizing agents can be used alone or in combination of two or more.
  • an anionic polar group-containing compound in producing the aqueous urethane resin dispersion, can also be used.
  • an anionic polar group-containing compound include compounds that consist of an organic acid having one or more active hydrogens and a neutralizing agent.
  • organic acids include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, and thiosulfonates. These anionic polar groups contained in the organic acid may be introduced alone or may be associated with a metal ion as in a chelate.
  • a cationic polar group-containing compound When producing the aqueous urethane resin dispersion, a cationic polar group-containing compound can also be used.
  • the cationic polar group-containing compound is, for example, a tertiary amine having one or more active hydrogens and one selected from the group consisting of a neutralizer for an inorganic acid, a neutralizer for an organic acid, and a quaternizing agent.
  • cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, and pyridinium salts can also be used as the cationic polar group-containing compound.
  • tertiary amines having one or more active hydrogens include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N-methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldipropanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis-(3-aminopropyl)-amine, and N-methyl-bis-(2-aminopropyl)-amine.
  • inorganic and organic acids examples include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.
  • Quaternizing agents include, for example, dimethyl sulfate, benzyl chloride, bromoacetamide, and chloroacetamide.
  • alkyl halides such as ethyl bromide, propyl bromide, and butyl bromide can also be used.
  • the aqueous urethane resin dispersion can be produced, for example, by sequentially carrying out the steps of reacting a polyol component containing a polyol having an acidic group with a polyisocyanate component in the presence or absence of a solvent to form a urethane prepolymer, neutralizing the acidic groups in the prepolymer with a neutralizing agent, dispersing the neutralized prepolymer in an aqueous medium, and reacting the prepolymer dispersed in the aqueous medium with a chain extender.
  • a catalyst can be used as necessary to promote the reaction and control the amount of by-products.
  • the film formed by the aqueous urethane resin dispersion described above (for example, a film formed by coating the aqueous urethane resin dispersion on a substrate) has excellent adhesion, flexibility, tactile feel, etc. Therefore, the aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather, exterior paint, interior paint, and coating agents.
  • the polyol component and the polyisocyanate component for forming the urethane resin may be stored, transported, etc. in separate containers as a two-liquid composition set.
  • the two-liquid composition set includes a first liquid containing at least the polyol component and a second liquid containing at least the polyisocyanate component.
  • a chain extender, a catalyst, a solvent, etc. are used, these may be contained in the first liquid and/or the second liquid, and may be mixed separately from the first liquid and the second liquid.
  • the two-liquid composition set can be suitably used, for example, as a coating agent, and can also be suitably used in the production of artificial leather, synthetic leather, exterior paint, interior paint, etc.
  • the two-liquid composition set is used as a coating agent, for example, after mixing the first liquid and the second liquid, the resulting mixed liquid is applied to a substrate and, if necessary, heated to form a coating film (for example, a cured film containing a urethane resin).
  • a coating film for example, a cured film containing a urethane resin
  • the two-liquid composition set as a coating agent it can be suitably used as a resin composition that does not use organic solvents in the manufacture of artificial leather, synthetic leather, etc., forming a polyurethane resin with excellent adhesion, flexibility, touch, etc.
  • the urethane resin-forming composition containing the above-mentioned polyol component and the above-mentioned polyisocyanate component, and the polyurethane resin composition containing the above-mentioned urethane resin are preferably used as an aqueous polyurethane resin emulsion, a polyurethane resin synthesized without a solvent, or a precursor thereof.
  • a molded body such as a coating film or film that is tough, has a reduced 100% modulus (good texture), and has a high softening temperature can be obtained, and can be suitably used for leather applications such as artificial leather and synthetic leather, and as a surface treatment agent for leather.
  • the 100% modulus is one of the indicators that quantify the moist, elastic, and luxurious feeling when touching synthetic leather, and if the value is within a certain numerical range, the urethane resin has good properties.
  • compositions, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment described above can be used in a coating composition that is preferably used as a clear coating for automobile exteriors and a coating for automobile interiors.
  • the composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment can also be preferably used in surface treatment of home appliances, OA (office automation) products, leather, synthetic leather, etc.
  • Example 1A 16.5 g of trimethylolpropane, 187.1 g of 1,6-hexanediol, 196.4 g of diethyl carbonate, 0.71 g of 3-ethyl-3-hydroxymethyloxetane, and 0.030 g of lithium acetylacetonate were mixed in a 1 L two-neck glass reactor (reactor A) equipped with a stirrer, a thermometer, a heating device, a fractionator filled with structured packing, and a cooler.
  • reactor A 1 L two-neck glass reactor
  • the resulting mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low boiling point components (such as alcohol derived from carbonate ester).
  • the distillate temperature was 77°C or higher and lower than 79°C.
  • the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150° C., and the reaction was further carried out at 0.5 kPa for 1.0 hour to obtain a composition (PCP-1A) containing compound (A-1).
  • Example 2A A composition (PCP-2A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 1.43 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 3A A composition (PCP-3A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 2.14 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 4A A composition (PCP-4A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 2.85 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 5A A composition (PCP-5A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 5.70 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 6A In the reactor A, 16.5 g of trimethylolpropane, 187.1 g of 1,6-hexanediol, 196.4 g of diethyl carbonate, and 0.030 g of lithium acetylacetonate were mixed. The obtained mixture was heated at 130 to 150°C (initial temperature 130°C, final temperature 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (such as alcohol derived from carbonate ester). The distillate temperature was 77°C or higher and lower than 79°C.
  • the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5 kPa for 35 hours to obtain a composition (PCP-6A) containing the compound (A-1).
  • composition (PCP-7A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.
  • composition (PCP-8A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 0.07 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-9A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 0.14 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-10A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 0.43 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-11A) containing the compound (A-1) was obtained in the same manner as in Example 1A, except that 7.13 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • ⁇ Calculation method for each composition> (Deemed average number of hydroxyl functional groups)
  • the deemed average hydroxyl functional number of the composition was calculated from the number average molecular weight and hydroxyl value obtained by GPC (Gel Permeation Chromatography) measurement.
  • GPC Gel Permeation Chromatography
  • the average hydroxyl functional number is calculated from the true number average molecular weight and the average hydroxyl value, but since it is difficult to calculate the true number average molecular weight of the composition, the number average molecular weight converted from the PPG calibration curve by GPC measurement is used and defined as the deemed average hydroxyl functional number.
  • the deemed average hydroxyl functional number is defined by the following formula.
  • Deemed average number of hydroxyl functional groups (average hydroxyl value of composition (mg KOH/g) ⁇ number average molecular weight (g/mol) calculated from a PPG calibration curve obtained by GPC measurement of the composition)/(56.11 (g KOH/mol) ⁇ 1000)
  • composition Analysis The composition was analyzed by the following procedure.
  • the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution.
  • Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution.
  • 1 H-NMR was measured for the obtained test solution using JNM-ECX400 manufactured by JEOL Ltd., and a 1 H-NMR spectrum was obtained with the TMS signal set at 0 ppm. The measurement was performed under the following conditions.
  • -conditions- ⁇ Resonance frequency 400MHz Pulse width: 45 degrees Waiting time: 5 seconds
  • Accumulation count 64
  • Sample solution concentration (TMS-containing deuterated chloroform) 3% by mass
  • the signal from 4.390 ppm to 4.500 ppm was taken as the signal (SC)
  • the signal from 3.618 ppm to 3.720 ppm was taken as the signal (SD)
  • the signal from 3.590 ppm to 3.618 ppm was taken as the signal (SE)
  • the signal from 0.700 ppm to 1.130 ppm was taken as the signal (SI) when R 2 of the groups represented by formulas (I) and (C) is a methyl group (when the polyhydric alcohol (e) is trimethylolethane)
  • the signal from 0.700 ppm to 1.000 ppm was taken as the signal (SI) when R 2 of the groups represented by formulas (I) and (C) is an ethyl group (when the polyhydric alcohol (e) is trimethylolpropane).
  • the baseline for the integral value measurement was a horizontal line drawn by comparing the spectral intensities in a specified spectral range and using the lowest spectral intensity as the reference.
  • the signal (SE) usually shows a single peak, but may be affected by trace amounts of moisture and split into two peaks. If a split peak is detected, it will deviate from the above integral range and an accurate CE cannot be obtained. Therefore, the integral value obtained from the signal (SE) is adopted when it shows a single peak.
  • a cured urethane coating (film) was prepared by the following method, and the physical properties (tensile properties, heat resistance, and low-temperature properties) of the obtained film were evaluated as samples.
  • -conditions- Processing equipment RHEOVIBRON DDV-01GP Dynamic Viscoelasticity (manufactured by Orientec Co., Ltd.) Range: -50 to 40°C Heating rate: 3°C/min Frequency: 35Hz Amplitude: 16 ⁇ m ⁇ Static tension: 5.00gf
  • An isocyanate-terminated urethane prepolymer was prepared by the following method, and the handleability (prepolymer viscosity) of the obtained isocyanate-terminated urethane prepolymer was evaluated as a sample.
  • compositions were overall evaluated on a scale of A, B, C, and D (A: very good, B: good, C: average, D: poor). The results are shown in Table 5.
  • Lithium acetylacetonate Sigma-Aldrich
  • JP-508 trade name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd.
  • DOTDL dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd.
  • methyl ethyl ketone manufactured by Maruzen Petrochemical Co., Ltd.
  • toluene manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.
  • BYK-331 silicon-based surface conditioner, manufactured by BYK Corporation; 2,2-dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.; isophorone diisocyanate: manufactured by Evonik Corporation.
  • Second Example Example 1B In the reactor A, 15.8 g of trimethylolpropane, 99.5 g of 1,6-hexanediol, 75.9 g of 1,4-butanediol, 208.9 g of diethyl carbonate, 0.68 g of 3-ethyl-3-hydroxymethyloxetane, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at 130 to 150°C (initial 130°C, final 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (such as alcohol derived from carbonate esters). The distillate temperature was 77°C or higher and lower than 79°C.
  • Example 2B A composition (PCP-2B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 1.36 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 3B A composition (PCP-3B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 2.73 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-4B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.
  • composition (PCP-5B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 6.82 g.
  • Example 4B A composition (PCP-6B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 0.60 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 5B A composition (PCP-7B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 2.73 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 6B A composition (PCP-8B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 4.80 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-9B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 0.34 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-10B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 0.50 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-11B) containing the compound (A-1) was obtained in the same manner as in Example 1B, except that 8.20 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • a cured urethane coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphate ester (JP508), and a dilution solvent were mixed in the proportions (units: g) shown in Table 7.
  • the obtained film was then used as a sample and evaluated for physical properties (tensile properties, texture properties, low-temperature properties) in the same manner as in Example 1. The results are shown in Table 7.
  • the handleability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (units: g) shown in Table 8. The results are shown in Table 8.
  • the overall evaluation of the composition was rated as A, B, C, or D (A: very good, B: good, C: average, D: poor). The results are shown in Table 9. ⁇ Overall evaluation> A: Each physical property and handling property was rated as A only. B: Each physical property and handling property was rated as 0, and included one B or C. C: Each physical property and handling property was rated as 0, and included two or more B or C. D: Each physical property and handling property was rated as 0.
  • Lithium acetylacetonate Sigma-Aldrich
  • JP-508 trade name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd.
  • DOTDL dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd.
  • Methyl ethyl ketone manufactured by Maruzen Petrochemical Co., Ltd.
  • Toluene manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.
  • BYK-331 silicon-based surface conditioner, manufactured by BYK Corporation; 2,2-dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Isophorone diisocyanate manufactured by Evonik Corporation
  • Example 1C In the reactor A, 16.5 g of trimethylolpropane, 93.6 g of 1,6-hexanediol, 93.6 g of 3-methyl-1,5-pentanediol, 196.4 g of diethyl carbonate, 0.77 g of 3-ethyl-3-hydroxymethyloxetane, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at 130 to 150°C (initial 130°C, final 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (such as alcohol derived from carbonate esters).
  • low-boiling components such as alcohol derived from carbonate esters
  • the distillate temperature was 77°C or higher and less than 79°C. Furthermore, the pressure in the flask was reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5 kPa for 1.0 hour to obtain a composition (PCP-1C) containing compound (A-1).
  • Example 2C A composition (PCP-2C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that 1.42 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 3C A composition (PCP-3C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that 3.00 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-4C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.
  • composition (PCP-5C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.17 g.
  • composition (PCP-6C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 7.30 g.
  • Example 4C A composition (PCP-7C) containing compound (A-1) was obtained in the same manner as in Example 1C, except that 2.20 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 5C A composition (PCP-8C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that 3.85 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 6C A composition (PCP-9C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that 6.50 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 7C In the reactor A, 16.5 g of trimethylolpropane, 93.6 g of 1,6-hexanediol, 93.6 g of 3-methyl-1,5-pentanediol, 196.4 g of diethyl carbonate, and 0.030 g of lithium acetylacetonate were mixed. The resulting mixture was heated at 130 to 150°C (initial 130°C, final 150°C) under normal pressure, and reacted for 1.5 hours while removing low-boiling components (such as alcohol derived from carbonate esters). The distillate temperature was 77°C or higher and lower than 79°C.
  • the pressure in the flask was gradually reduced to 0.5 kPa over 0.5 hours at a reaction temperature of 150°C, and the reaction was further carried out at 0.5 kPa for 35 hours to obtain a composition (PCP-10C) containing the compound (A-1).
  • composition (PCP-11C) containing the compound (A-1) was obtained in the same manner as in Example 1C, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.55 g.
  • a cured urethane coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethane catalyst, a phosphate ester (JP508), and a dilution solvent were mixed in the proportions (units: g) shown in Tables 8 and 9.
  • the obtained film was then used as a sample to evaluate its physical properties (tensile properties, texture properties, low-temperature properties) in the same manner as in Example 1. The results are shown in Table 11.
  • the handleability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (units: g) shown in Table 12. The results are shown in Table 12.
  • the overall evaluation of the composition was rated as A, B, C, or D (A: very good, B: good, C: fair, D: poor). The results are shown in Table 13. ⁇ Overall evaluation> A: Each physical property and handling property was rated as A only. B: Each physical property and handling property was rated as 0, and included one B or C. C: Each physical property and handling property was rated as 0, and included two or more B or C. D: Each physical property and handling property was rated as 0.
  • Lithium acetylacetonate Sigma-Aldrich
  • JP-508 trade name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd.
  • DOTDL dioctyltin dilaurate, manufactured by Kishida Chemical Industry Co., Ltd.
  • Methyl ethyl ketone manufactured by Maruzen Petrochemical Co., Ltd.
  • Toluene manufactured by Fujifilm Wako Pure Chemical Industries Co., Ltd.
  • BYK-331 silicon-based surface conditioner, manufactured by BYK Corporation; 2,2-dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Isophorone diisocyanate manufactured by Evonik Corporation
  • Fourth Embodiment Example 1D 371.6 g of PCD-1, 128.2 g of Plaxel 305, 1.35 g of 3-ethyl-3-hydroxymethyloxetane, and 0.08 g of lithium acetylacetonate were mixed in a 0.5 L four-neck glass reactor (reactor B) equipped with a stirrer, thermometer, heating device, and cooler. The mixture was heated at 190° C. under normal pressure and reacted for 6 hours. A composition (PCP-1D) containing compound (A-1) was obtained.
  • Example 2D A composition (PCP-2D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 2.91 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 3D A composition (PCP-3D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 5.42 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 4D 371.6 g of PCD-1, 128.2 g of Plaxel 305, and 0.08 g of lithium acetylacetonate were mixed in a reactor B. The mixture was heated at 190° C. under normal pressure and reacted for 35 hours to obtain a composition (PCP-4D) containing compound (A-1).
  • composition (PCP-5D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0 g.
  • composition (PCP-6D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.39 g.
  • composition (PCP-7D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.93 g.
  • composition (PCP-8D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 13.5 g.
  • Example 5D A composition (PCP-10D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 0.97 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 6D A composition (PCP-11D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 1.05 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 7D A composition (PCP-12D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 1.20 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 8D A composition (PCP-13D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 8.00 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • Example 9D A composition (PCP-14D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that 10.00 g of 3-ethyl-3-hydroxymethyloxetane was added.
  • composition (PCP-15D) containing the compound (A-1) was obtained in the same manner as in Example 1D, except that the amount of 3-ethyl-3-hydroxymethyloxetane was 0.19 g.
  • a cured urethane coating (film) was obtained in the same manner as in Example 1, except that the composition obtained above, a polyisocyanate component (C-2612), a urethanization catalyst, a phosphoric ester (JP508), and a dilution solvent were mixed in the proportions (units: g) shown in Table 15.
  • the obtained film was then used as a sample and evaluated for physical properties (tensile properties, texture properties, low-temperature properties) in the same manner as in Example 1. The results are shown in Table 15.
  • the handleability (viscosity of isocyanate-terminated urethane prepolymer) was evaluated in the same manner as in Example 1, except that the composition obtained above, N-980N, 1,6-hexanediol, 2,2-dimethylolpropanoic acid (hydrophilizing agent), isophorone diisocyanate (polyisocyanate), and methyl ethyl ketone (organic solvent) were charged in the amounts (units: g) shown in Table 16. The results are shown in Table 16.
  • the overall evaluation of the composition was rated as A, B, C, or D (A: very good, B: good, C: fair, D: poor). The results are shown in Table 17. ⁇ Overall evaluation> A: Each physical property and handling property was rated as A only. B: Each physical property and handling property was rated as 0, and included one B or C. C: Each physical property and handling property was rated as 0, and included two or more B or C. D: Each physical property and handling property was rated as 0.
  • Tosoh Corporation JP-508 trade name, 2-ethylhexyl acid phosphate, Johoku Chemical Industry Co., Ltd.
  • DOTDL dioctyltin dilaurate
  • Methyl ethyl ketone Maruzen Petrochemical Co., Ltd.
  • Toluene Fujifilm Wako Pure Chemical Industries Co., Ltd.
  • BYK-331 silicon-based surface conditioner, BYK Corporation 2,2-dimethylolpropionic acid: Tokyo Chemical Industry Co., Ltd. Isophorone diisocyanate: Evonik Corporation

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Polyurethanes Or Polyureas (AREA)
PCT/JP2024/007151 2023-03-31 2024-02-27 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 Ceased WO2024202836A1 (ja)

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EP24778977.9A EP4674889A1 (en) 2023-03-31 2024-02-27 Composition and method for producing same, urethane resin, aqueous urethane resin dispersion, and coating agent
CN202480022994.9A CN121002091A (zh) 2023-03-31 2024-02-27 组合物及其制造方法、聚氨酯树脂、水性聚氨酯树脂分散体及涂覆剂
KR1020257034304A KR20250159254A (ko) 2023-03-31 2024-02-27 조성물 및 그 제조 방법, 유레테인 수지, 수성 유레테인 수지 분산체, 및 코팅제
JP2024534414A JP7601290B1 (ja) 2023-03-31 2024-02-27 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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WO2025204695A1 (ja) * 2024-03-28 2025-10-02 Ｕｂｅ株式会社 オキセタニル変性ポリカーボネートポリオール

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JPH03220233A (ja) 1989-10-11 1991-09-27 Daicel Chem Ind Ltd ポリカーボネートポリオール
JP2011219750A (ja) * 2010-03-25 2011-11-04 Ube Industries Ltd 分子末端にオキセタンを有するポリカーボネート及びその製造方法
JP2012184380A (ja) 2011-03-08 2012-09-27 Ube Industries Ltd ポリウレタン化合物、それを含む組成物、及びこれらの硬化物
JP2019035073A (ja) * 2017-08-10 2019-03-07 三菱ケミカル株式会社 ポリカーボネートポリオール及びその製造方法
JP2019123871A (ja) * 2018-01-17 2019-07-25 宇部興産株式会社 高分岐ポリカーボネートポリオール組成物
WO2022080491A1 (ja) * 2020-10-16 2022-04-21 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、並びに、水性ウレタン樹脂分散体
WO2022244850A1 (ja) * 2021-05-19 2022-11-24 東ソー株式会社 ポリウレタン樹脂組成物、硬化物、人工皮革、合成皮革、および皮革用表面処理剤
WO2023199756A1 (ja) * 2022-04-15 2023-10-19 東ソー株式会社 化合物及びその製造方法、組成物、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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JPH03220233A (ja) 1989-10-11 1991-09-27 Daicel Chem Ind Ltd ポリカーボネートポリオール
JP2011219750A (ja) * 2010-03-25 2011-11-04 Ube Industries Ltd 分子末端にオキセタンを有するポリカーボネート及びその製造方法
JP2012184380A (ja) 2011-03-08 2012-09-27 Ube Industries Ltd ポリウレタン化合物、それを含む組成物、及びこれらの硬化物
JP2019035073A (ja) * 2017-08-10 2019-03-07 三菱ケミカル株式会社 ポリカーボネートポリオール及びその製造方法
JP2019123871A (ja) * 2018-01-17 2019-07-25 宇部興産株式会社 高分岐ポリカーボネートポリオール組成物
WO2022080491A1 (ja) * 2020-10-16 2022-04-21 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、並びに、水性ウレタン樹脂分散体
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Publication number Priority date Publication date Assignee Title
WO2025204695A1 (ja) * 2024-03-28 2025-10-02 Ｕｂｅ株式会社 オキセタニル変性ポリカーボネートポリオール

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TW202513636A (zh) 2025-04-01
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JPWO2024202836A1 (https=) 2024-10-03
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