Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—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
  • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
  • C08G18/08—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
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
  • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4202—Two or more polyesters of different physical or chemical nature
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
  • C08G18/4269—Lactones
  • C08G18/4277—Caprolactone and/or substituted caprolactone
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • 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
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • 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
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/18—Block or graft polymers
  • C08G64/183—Block or graft polymers containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
  • C08G64/20—General preparatory processes
  • C08G64/30—General preparatory processes using carbonates
  • C08G64/305—General preparatory processes using carbonates and alcohols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
• • 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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
  • D06N3/146—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes characterised by the macromolecular diols used
• • 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
• • 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
  • D06N2203/00—Macromolecular materials of the coating layers
  • D06N2203/06—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N2203/068—Polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N2211/00—Specially adapted uses
  • D06N2211/12—Decorative or sun protection articles
  • D06N2211/28—Artificial leather

Definitions

• the present invention relates to a polycarbonate diol composition.
• Polyurethane resins have traditionally been used in a wide range of areas, including synthetic leather, artificial leather, adhesives, furniture paints, and automotive paints.
• Polyethers, polyesters, and polycarbonates are used as polyol components to be reacted with isocyanate among raw materials of polyurethane resins.
• durability of polyurethane resins such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, and scratch resistance.
• polyether polyol as a polyol component generally has a low viscosity. Therefore, polyurethanes using polyether polyols are said to be excellent in flexibility and hydrolysis resistance, but inferior in heat resistance and weather resistance. Polyurethanes using polyester polyols have improved heat resistance and weather resistance, but are inferior in hydrolysis resistance. On the other hand, polyurethane using polycarbonate polyol is considered to be the best durability grade in terms of durability such as heat resistance, chemical resistance and hydrolysis resistance, but there is room for improvement in handling due to its high viscosity.
• Patent Document 1 describes a production method for synthesizing a copolymerized polycarbonate diol by transesterifying a polycarbonate diol
• Patent Document 2 describes a polyester polyol having a specific structure
• Patent Document 3 discloses a coating composition using a specific polycarbonate diol composition.
• the present invention has been made in view of the above circumstances, and provides a polycarbonate diol composition that is excellent in quality stability, less in coloration, and excellent in compatibility with other polyols, solvents, and the like. With the goal.
• the gist of the present invention is as follows. [1] Including a repeating structural unit represented by the following general formula (I), a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula A polycarbonate diol composition containing at least one repeating structural unit selected from the group consisting of repeating structural units represented by (IV) and satisfying the following formula (Formula 1). ...
• R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a hetero atom When there is more than one, R 11 may be the same or different.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 21 in the case may be the same or different, and n21 is an arbitrary integer.) ...
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 31 in the case may be the same or different.) ...
• R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a hetero atom When there is more than one, R 11 may be the same or different.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 21 in the case may be the same or different, and n21 is an arbitrary integer.) ...
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 31 in the case may be the same or different.) ...
• R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic is a hydrocarbon group.When there are a plurality of R 41 and R 42 , they may be the same or different.) [3] The content of the repeating structural unit represented by the general formula (I) is 5% by mass or more and 95% by mass or less with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV). The polycarbonate diol composition according to [1].
• the content of the repeating structural unit represented by the general formula (I) is 40% by mass or more and 90% by mass or less with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV).
• the polycarbonate diol composition according to any one of [1] to [5] which has a peroxide content of 10 meq/kg or less.
• a synthetic leather comprising the polyurethane according to [11] or [12].
• the polycarbonate diol composition of the present invention has excellent quality stability, little coloration, and excellent compatibility with solvents and other polyols.
• this embodiment the form for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. It should be noted that the present invention is not limited to the following description, and various modifications can be made within the scope of the gist of the present invention.
• the first polycarbonate diol composition of the present embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also simply referred to as “structural unit (I)”), and further comprises a repeating structural unit represented by the following general formula (II): ) (hereinafter simply referred to as “structural unit (II)”), a repeating structural unit represented by the following general formula (III) (hereinafter simply referred to as “structural unit (III)” ), and at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (IV) (hereinafter also simply referred to as “structural unit (IV)”), (Formula 1) is satisfied. ...
• R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a hetero atom When there is more than one, R 11 may be the same or different.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 21 in the case may be the same or different, and n21 is an arbitrary integer.) ...
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 31 in the case may be the same or different.) ...
• the polycarbonate diol composition of the present embodiment has excellent quality stability and excellent compatibility with solvents and other polyols.
• the second polycarbonate diol composition of the present embodiment contains a repeating structural unit represented by the following general formula (I) (hereinafter also simply referred to as “structural unit (I)”), and further comprises the following general formula: A repeating structural unit represented by (II) (hereinafter also simply referred to as “structural unit (II)”), a repeating structural unit represented by the following general formula (III) (hereinafter simply referred to as “structural unit (III)”) ), and at least one repeating structural unit selected from the group consisting of a repeating structural unit represented by the following general formula (IV) (hereinafter also simply referred to as “structural unit (IV)”),
• the content of the repeating structural unit represented by the general formula (I) is 40% by mass or more with respect to the total mass of the repeating structural units represented by the general formulas (I) to (IV), and the cloud point
• the titration amount in the titration method is 4.0 mL or more and 9.5 mL or less
• R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a hetero atom When there is more than one, R 11 may be the same or different.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 21 in the case may be the same or different, and n21 is an arbitrary integer.) ...
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 31 in the case may be the same or different.
• R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic is a hydrocarbon group.When there are a plurality of R 41 and R 42 , they may be the same or different.
• the polycarbonate diol composition of the present embodiment has excellent compatibility with solvents and other polyols.
• the polycarbonate diol composition of the present embodiment is not particularly limited in production method, and is a copolymer of structural unit (I) and at least one type of structural unit among structural units (II) to (IV). or each may exist independently.
• R 11 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 15 carbon atoms, and a heteroatom is may have. When there is a plurality of R 11 , they may be the same or different.
• the divalent linear aliphatic hydrocarbon group for R 11 has 2 to 15 carbon atoms, preferably 3 to 12 carbon atoms, more preferably 3 to 10 carbon atoms.
• divalent linear aliphatic hydrocarbon group for R 11 are not particularly limited, but include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptylene group and octylene group. etc. From the viewpoint of versatility, trimethylene group, butylene group, pentylene group, hexylene group and decamethylene group are preferred.
• the divalent branched aliphatic hydrocarbon group for R 11 has 3 to 15 carbon atoms, preferably 3 to 12 carbon atoms, and more preferably 3 to 10 carbon atoms.
• divalent branched aliphatic hydrocarbon group for R 11 are not particularly limited, but examples include isopropylene group, isobutylene group, tert-butylene group, isopentylene group, and 2,2-dimethyltrimethylene group. , an isohexylene group, an isoheptylene group, an isooctylene group, and the like. Among them, an isobutylene group, an isopentylene group, or an isohexylene group is preferable from the viewpoint of versatility.
• the divalent cycloaliphatic hydrocarbon group for R 11 has from 3 to 15 carbon atoms, preferably from 6 to 15 carbon atoms, and more preferably from 6 to 10 carbon atoms.
• divalent cyclic aliphatic hydrocarbon group for R 11 are not particularly limited, but include, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and the like. Among them, a cyclohexylene group is preferable from the viewpoint of versatility.
• the divalent aromatic hydrocarbon group for R 11 has from 6 to 15 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 6 to 10 carbon atoms.
• divalent aromatic hydrocarbon group for R 11 are not particularly limited, but include, for example, a phenylene group and a naphthylene group.
• heteroatom for R 11 are not particularly limited, but examples include boron, oxygen, nitrogen, phosphorus, sulfur, and five-membered heterocyclic structures such as oxolane, thiolane, and azolidine, oxane, and pyridine. It may have a six-membered heterocyclic structure such as
• R 11 is preferably a divalent straight-chain aliphatic hydrocarbon group having 3 to 10 carbon atoms or a divalent branched aliphatic hydrocarbon group having 3 to 10 carbon atoms.
• a divalent linear aliphatic hydrocarbon group having a number of 4 or more and 6 or less is more preferable, and a divalent linear aliphatic hydrocarbon group such as a butylene group, a pentylene group and a hexylene group is even more preferable.
• the polycarbonate diol composition of the present embodiment at least part of the polycarbonate diol is a divalent linear or branched aliphatic having 2 to 15 carbon atoms in R 11 in the general formula (I). At least two or more selected from the group consisting of hydrocarbon groups are preferred. In this case, a polycarbonate diol composition that is liquid at room temperature tends to be obtained.
• both ends of the molecule are preferably hydroxyl groups.
• the molecules having a polycarbonate structure contained in the polycarbonate diol composition of the present embodiment preferably have hydroxyl groups at both ends. That is, the molecule having a polycarbonate structure contained in the polycarbonate diol composition of the present embodiment is preferably polycarbonate diol. Due to impurities in various raw materials used in the production of the polycarbonate diol composition, terminal structures produced by-products in the production of the polycarbonate diol composition, or the like, or the urethanization reaction rate and state in the application of the polycarbonate diol composition For control purposes, some of the terminal hydroxyl groups may be converted to alkyl or aryl groups that do not react with isocyanate groups.
• the present embodiment also includes the case where 100 mol % of both ends of the terminal groups of the polycarbonate diol are not strictly hydroxyl groups.
• the ratio of hydroxyl groups to the total molar amount of terminal groups is preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 98 mol% or more.
• the structure of both ends of the polycarbonate diol contained in the polycarbonate diol composition is confirmed according to, for example, the method for measuring the ratio of primary terminal OH described in Japanese Patent No. 3874664 (reference document 1). be able to.
• the solvent for collecting the fraction other than ethanol, solvents such as tetrahydrofuran, acetone, and methanol can be used.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. When there is more than one R 21 , they may be the same or different.
• the divalent linear aliphatic hydrocarbon group for R 21 has 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms.
• divalent linear aliphatic hydrocarbon group for R 21 are not particularly limited, but include ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptylene group and octylene group. etc.
• the divalent branched aliphatic hydrocarbon group for R 21 has 3 or more and 20 or less carbon atoms, preferably 3 or more and 12 or less, and more preferably 3 or more and 6 or less.
• divalent branched aliphatic hydrocarbon group for R 21 are not particularly limited, but examples include an isopropylene group, an isobutylene group, a tert-butylene group, an isopentylene group, and a 2,2-dimethyltrimethylene group. , an isohexylene group, an isoheptylene group, an isooctylene group, and the like.
• the divalent cycloaliphatic hydrocarbon group for R 21 has from 6 to 20 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 6 to 8 carbon atoms.
• divalent cyclic aliphatic hydrocarbon group for R 21 are not particularly limited, but include, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group and the like.
• the divalent aromatic hydrocarbon group for R 21 has from 6 to 15 carbon atoms, preferably from 6 to 12 carbon atoms, and more preferably from 6 to 10 carbon atoms.
• divalent aromatic hydrocarbon group for R 21 examples include, but are not particularly limited to, a phenylene group, a naphthylene group, and the like.
• R 21 is preferably a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms (that is, an alkylene group), and a divalent group having 2 to 6 carbon atoms. and/or a divalent branched aliphatic hydrocarbon group having 3 or more and 6 or less carbon atoms.
• n21 represents the number of repetitions of the structure ( -R21 -O-).
• n21 is an arbitrary integer, and the average value of n21 in the entire polycarbonate diol composition of the present embodiment is preferably 12 or more, more preferably 12 or more and 70 or less. , more preferably 12 or more and 60 or less, even more preferably 15 or more, and particularly preferably 15 or more and 50 or less.
• n21 in the entire polycarbonate diol composition of the present embodiment When the average value of n21 in the entire polycarbonate diol composition of the present embodiment is equal to or higher than the above lower limit, there is a tendency to obtain a polyurethane with even better flexibility and low-temperature flexibility. Further, when the average value of n21 in the entire polycarbonate diol composition of the present embodiment is equal to or less than the above upper limit value, the viscosity of the polycarbonate diol composition tends to be lower.
• n21 can be obtained by subjecting the polycarbonate diol composition to alkali decomposition to extract the raw material diol component, and then performing GC-MS measurement, LC-MS measurement and gel permeation chromatography (GPC) measurement on the component. Specifically, it can be determined by the method described in Examples below.
• the structural unit (II) is preferably a polyoxyalkylene structure.
• preferred oxyalkylene groups contained in the structural unit (II) are not particularly limited, but include, for example, an oxyethylene group, an oxy-1-methylethylene group, an oxytetramethylene group, and an oxy-2,2-dimethyltrimethylene group. etc. Among them, a structure containing an oxy-1-methylethylene group is preferred, and an oxy-1-methylethylene group and an oxyethylene group are particularly preferred.
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. When there is a plurality of R 31 , they may be the same or different.
• R 31 in general formula (III) is not particularly limited, but examples thereof include a linear or branched alkylene group having 2 to 20 carbon atoms. Specifically, but not limited to, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, propylene group, isobutylene group, 2-methyl Tetramethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, isononamethylene group, 2-methylnonamethylene group and the like can be mentioned.
• R 31 in general formula (III) is not particularly limited, but examples thereof include a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms. Specifically, but not limited to, for example, a cyclopentylene group, a cyclohexylene group, a 1,2-dimethylenecyclopentane group, a 1,3-dimethylenecyclopentane group, a 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group and the like.
• R 31 in general formula (III) is not particularly limited, but examples thereof include a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Specifically, but not limited to, for example, phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group, 1,4-dimethylenebenzene group, naphthylene group, 4,4′- A methylenediphenylene group, a 2,2-diphenylenepropane group, and the like can be mentioned.
• R 31 is preferably a pentamethylene group from the viewpoint of improving stain resistance and solvent resistance when made into polyurethane, and easiness in obtaining the raw material cyclic ester compound.
• each R 41 is independently a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. be. When there is a plurality of R 41 , they may be the same or different.
• R 41 in general formula (IV) is not particularly limited, but examples thereof include a linear or branched alkylene group having 2 to 20 carbon atoms. Specifically, but not limited to, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, propylene group, isobutylene group, 2-methyl Tetramethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, isononamethylene group, 2-methylnonamethylene group and the like can be mentioned.
• R 41 in general formula (IV) is not particularly limited, but examples thereof include a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms. Specifically, but not limited to, for example, a cyclopentylene group, a cyclohexylene group, a 1,2-dimethylenecyclopentane group, a 1,3-dimethylenecyclopentane group, a 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group and the like.
• R 41 in general formula (IV) is not particularly limited, but examples thereof include a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Specifically, but not limited to, for example, phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group, 1,4-dimethylenebenzene group, naphthylene group, 4,4′- A methylenediphenylene group, a 2,2-diphenylenepropane group, and the like can be mentioned.
• R 42 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. R 42 when there is more than one may be the same or different.
• R 42 in general formula (IV) is not particularly limited, but examples thereof include a linear or branched alkylene group having 2 to 20 carbon atoms. Specifically, but not limited to, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, propylene group, isobutylene group, 2-methyl Tetramethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, isononamethylene group, 2-methylnonamethylene group and the like.
• R 42 in general formula (IV) is not particularly limited, but examples thereof include a substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms. Specifically, but not limited to, for example, a cyclopentylene group, a cyclohexylene group, a 1,2-dimethylenecyclopentane group, a 1,3-dimethylenecyclopentane group, a 1,2-dimethylenecyclohexane group, 1,3-dimethylenecyclohexane group, 1,4-dimethylenecyclohexane group, 4,4'-methylenedicyclohexylene group, 2,2-dicyclohexylenepropane group and the like.
• R 42 in general formula (IV) is not particularly limited, but examples thereof include a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Specifically, but not limited to, for example, phenylene group, 1,2-dimethylenebenzene group, 1,3-dimethylenebenzene group, 1,4-dimethylenebenzene group, naphthylene group, 4,4′- A methylenediphenylene group, a 2,2-diphenylenepropane group, and the like can be mentioned.
• the polycarbonate diol composition of the present embodiment has a repeating structural unit represented by the following general formula (II), a repeating structural unit represented by the following general formula (III), and a repeating structural unit represented by the following general formula (IV). It contains at least one repeating structural unit selected from the group consisting of repeating structural units.
• R 21 is a divalent linear, branched or cyclic aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 20 carbon atoms. R 21 in the case may be the same or different, and n21 is an arbitrary integer.) ...
• R 31 is a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group. R 31 in the case may be the same or different.
• R 41 and R 42 are each independently a divalent linear, branched or cyclic aliphatic hydrocarbon group having 2 to 20 carbon atoms, or an aromatic is a hydrocarbon group.When there are a plurality of R 41 and R 42 , they may be the same or different.
• the terminal structures of the structural units (II) to (IV) are terminal structures in which one terminal is bonded to a carbonate group and the other terminal is bonded to a hydroxyl group.
• it may have a terminal structure in which both terminals are bound to carbonate groups, or a terminal structure in which both terminals are bound to hydroxyl groups.
• the terminal structure of the structural units (II) to (IV) is a terminal structure in which one end is bonded to a carbonate group and the other end is bonded to a hydroxyl group.
• a mixture of a terminal structure in which both terminals are bonded to carbonate groups and a terminal structure in which both terminals are bonded to hydroxyl groups may be used.
• the polycarbonate diol composition of the present embodiment preferably contains the structural unit (II) or (IV) among the structural units (II) to (IV) from the viewpoint of flexibility, low-temperature properties, and heat and humidity resistance. , more preferably contains the structural unit (II).
• the second polycarbonate diol composition of the present embodiment has a titration amount of 4.0 mL or more and 9.5 mL or less, preferably 4.0 mL or more and 8.5 mL or less, by the turbidity point titration method.
• the titration amount in the turbidity point titration method is obtained by dissolving the polycarbonate diol composition in butyl acetate, which is a good solvent, and titrating the resulting solution with hexane, which is a poor solvent. is the titration amount at the time of If it is insoluble in butyl acetate, it may be dissolved in acetone. Specifically, it can be determined by the method described in Examples below.
• This turbidity point titration evaluates solubility in solvents, and differences appear depending on the type, molecular weight, and structure of the polyol. In general, the smaller the molecular weight, the higher the solubility in a solvent, and the solubility varies depending on the functional groups contained. Therefore, with respect to polyols, there is a difference in solubility between a blend of two or more types of polyols and a case where the structure is changed by reaction.
• the second polycarbonate diol composition of the present embodiment has a titration amount of 4.0 mL or more and 9.5 mL or less by the turbidity point titration method, preferably 4.0 mL or more and 8.5 mL or less, and 4.0 mL or more. It is more preferably 7.6 mL or less, and even more preferably 4.1 mL or more and 7.4 mL or less.
• the titration amount by the turbidity point titration method is at least the above lower limit, the compatibility of the polycarbonate diol composition with the solvent and raw materials for synthesizing polyurethane is improved, and the titration amount by the turbidity point titration method is above the above. It is preferable that it is not more than the upper limit because a polyurethane having excellent balance of low-temperature flexibility and durability such as chemical resistance and moist heat resistance can be obtained.
• the method for controlling the titration amount by the turbidity point titration method within the above range is not particularly limited.
• a method of adjusting the reaction time and a method of appropriately adjusting the oxygen concentration during mixing and stirring are also exemplified.
• the progress of the transesterification reaction can be evaluated, so by setting a target value for the titer amount in the turbidity point titration method, the variation in the transesterification reaction depending on the production lot can be reduced, and the quality can be improved. There is a tendency to obtain a polycarbonate diol composition excellent in stabilization.
• the number average molecular weight can be calculated from the hydroxyl value of the polycarbonate diol composition using the method described in the examples below.
• polycarbonate diols have low solubility in solvents, so y tends to decrease as x increases. It is speculated that the more randomly the repeating structural units represented by the general formulas (I) to (IV) and the repeating structural units represented by the general formula (I) exist, the greater the titer of turbidity point titration. .
• the method for obtaining the polycarbonate diol composition satisfying the above formula (formula 1) is not particularly limited, but for example, a method of appropriately setting the reaction time until the modification progresses sufficiently can be mentioned.
• the content of the structural unit (I) is preferably 5% by mass or more and 95% by mass or less, and 20% by mass, based on the total mass of the structural units (I) to (IV). 90% by mass or less is more preferable, and 40% by mass or more and 90% by mass or less is even more preferable.
• the content of the structural unit (I) is at least the above lower limit, a polyurethane having excellent durability such as chemical resistance and moist heat resistance can be obtained, which is preferable.
• the content of the structural unit (I) is equal to or less than the above upper limit, the viscosity of the polycarbonate diol composition tends to be low.
• the content of structural unit (I) can be measured by the method described in Examples below.
• the number average molecular weight of the polycarbonate diol composition of the present embodiment is preferably 250 to 10,000, more preferably 400 to 8,000, even more preferably 500 to 5,000, and particularly preferably 500 to 3,000.
• the number average molecular weight of the polycarbonate diol composition of the present embodiment is equal to or less than the above upper limit, the viscosity tends to decrease and the handleability during polyurethane production tends to improve. Further, when the number average molecular weight is at least the above lower limit, the flexibility of the polyurethane produced using the polycarbonate diol composition of the present embodiment tends to be excellent.
• the method for controlling the number average molecular weight of the polycarbonate diol composition of the present embodiment within the above range is not particularly limited.
• the number average molecular weight of the polycarbonate diol composition can be measured by the method described in Examples below.
• the acid value of the polycarbonate diol composition of the present embodiment is preferably 0.001 mg-KOH/g or more and 0.8 mg-KOH/g or less, and is preferably 0.005 mg-KOH/g or more and 0.6 mg-KOH/g. It is more preferably 0.01 mg-KOH/g or more and 0.6 mg-KOH/g or less. Since it is difficult to remove all acidic compounds derived from raw materials, catalysts, additives, etc., it is preferable from the viewpoint of productivity of the polycarbonate diol composition that the acid value is at least the above lower limit. When it is equal to or less than the above upper limit, it tends to be possible to reduce the occurrence of coloring.
• the method for controlling the acid value of the polycarbonate diol composition within the above range is not particularly limited. There is a method of appropriately selecting the addition.
• the acid value of the polycarbonate diol composition can be measured by the method described in Examples below.
• the peroxide content (hereinafter also referred to as “peroxide value”) of the polycarbonate diol composition of the present embodiment is preferably 10 meq/kg or less, more preferably 3 meq/kg or less.
• the polycarbonate diol composition of the present embodiment has a peroxide value of 10 meq/kg or less, coloring tends to be suppressed.
• the lower limit of the peroxide value of the polycarbonate diol composition of the present embodiment is not particularly limited, it is, for example, 0.01 meq/kg.
• Examples of the method for measuring the peroxide value include a sodium thiosulfate titration method in which potassium iodide is allowed to act on oxidized fats and oils in an acidic manner to obtain liberated iodine by a titration method. It can be easily measured using a test paper for price measurement (trade name: “POV test paper”, manufactured by Shibata Chemical Co., Ltd.). Specifically, it can be measured by the method described in Examples below.
• the method for controlling the peroxide value of the polycarbonate diol composition within the above range is not particularly limited. Sometimes, there are a method of setting the oxygen concentration to 0.5% or less, and a method of setting the nitrogen flow rate during production to 0.1 L/min or more and 50 L/min or less, and the above methods may be combined.
• the Hazen color number (hereinafter also referred to as "APHA") value (APHA value: according to JIS K0071-1 (2017)) of the polycarbonate diol composition of the present embodiment is preferably 100 or less, more preferably 60 or less. , 50 or less.
• the lower limit of the APHA value is not particularly limited, it is 0, for example.
• a polycarbonate diol composition satisfying such an APHA value can be produced by adjusting the APHA of the raw material to be used to 100 or less. It becomes more effective when the concentration is 0.5% or less.
• the APHA value can be measured by the method described in Examples below.
• the method for producing the polycarbonate diol composition of the present embodiment is not particularly limited as long as it satisfies the above characteristics.
• I-1) an ether diol represented by the following general formula (II-1)
• ether diol (II-1) an ether diol represented by the following general formula (II-1)
• polycaprolactone diol (III-1) represented by III-1) hereinafter sometimes referred to as "lactone diol (III-1)
• polyester diol represented by the following general formula (IV-1) hereinafter sometimes referred to as "ester diol (IV-1)
• a method of performing an ester exchange reaction using at least one selected from the group consisting of polycarbonate diol (I-1) and a cyclic ester compound A method of reacting is mentioned.
• Polycarbonate Diol (I-1) As the polycarbonate diol (I-1) used for producing the polycarbonate diol composition of the present embodiment, any polycarbonate diol having a structure represented by the above general formula (I-1) may be used.
• the method for producing the polycarbonate diol (I-1) is not particularly limited, and known methods can be employed.
• a polycarbonate diol (I-1) can be obtained by reacting a carbonate compound and a diol compound in the presence of a transesterification catalyst.
• Carbonate compound examples of carbonate compounds used for producing polycarbonate diol (I-1) include, but are not limited to, alkylene carbonates, dialkyl carbonates, diaryl carbonates, and the like.
• the alkylene carbonate is not particularly limited, but examples thereof include ethylene carbonate, trimethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 1,2-pentylene carbonate and the like. be done.
• the dialkyl carbonate is not particularly limited, but includes, for example, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate and the like.
• the diaryl carbonate is not particularly limited, but includes, for example, diphenyl carbonate.
• ethylene carbonate, dimethyl carbonate, diethyl carbonate, and diphenyl carbonate are preferable as the carbonate compound used for producing the polycarbonate diol (I-1), and ethylene carbonate is more preferable.
• the diol compound used for producing the polycarbonate diol (I-1) is not limited to the following, but examples thereof include linear diols, branched diols, cyclic diols, and diols having an aromatic ring.
• linear diols include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptane. diol, 1,8-octanediol, 1,9-nanodiol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like.
• branched diols include, but are not limited to, 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol. , 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and the like.
• the cyclic diol is not particularly limited, but includes, for example, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane and the like.
• the diol having an aromatic ring is not particularly limited, but examples include p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, 2,2-bis[(4-hydroxyethoxy) phenyl]propane and the like.
• linear diols or branched diols having 3 to 10 carbon atoms are preferable, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, 1 ,9-nanodiol, 1,10-decanediol, 2-methyl-1,3-propanediol and 3-methyl-1,5-pentanediol are preferred, and 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol is more preferred.
• a transesterification catalyst can be used in the production of polycarbonate diol (I-1) as a starting material.
• the catalyst can be selected from common transesterification reaction catalysts.
• transesterification catalysts include, but are not limited to, alkali metals and alkaline earth metals, alcoholates thereof, hydrides thereof, oxides thereof, amides thereof, hydroxides thereof and salts thereof.
• the salts of alkali metals and alkaline earth metals are not particularly limited, but examples include carbonates, nitrogen-containing borates, basic salts with organic acids, and the like.
• alkali metals include, but are not limited to, lithium, sodium, and potassium.
• alkaline earth metals include, but are not limited to, magnesium, calcium, strontium, and barium.
• the transesterification catalyst using a metal other than alkali metals and alkaline earth metals is not particularly limited, but for example, metals other than alkali metals and alkaline earth metals, salts thereof, alcoholates thereof, and Examples include organic compounds containing metals.
• metals other than alkali metals and alkaline earth metals are not particularly limited, but include aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, zirconium, niobium , molybdenum, ruthenium, rhodium, palladium, silver, indium, tin, antimony, tungsten, rhenium, osmium, iridium, platinum, gold, thallium, lead, bismuth, ytterbium, and the like.
• transesterification catalysts can be used singly or in combination of two or more.
• metals selected from the group consisting of titanium, zirconium, tin, lead and ytterbium, salts thereof, alkoxides thereof, or organic compounds containing these metals are preferred.
• one or more metals selected from the group consisting of magnesium, titanium, ytterbium, tin and zirconium are more preferable.
• transesterification catalysts include, but are not limited to, magnesium organic compounds, lead organic compounds, titanium organic compounds, and the like.
• the organic compound of magnesium is not particularly limited, but examples include magnesium acetate tetrahydrate, magnesium acetate anhydrate, and the like.
• the organic compound of lead is not particularly limited, but examples include lead acetate trihydrate, tetraphenyl lead, and lead stearate.
• the organic compound of titanium is not particularly limited, but examples thereof include titanium tetra-n-butoxide, titanium tetra-n-propoxide, titanium tetraisopropoxide and the like.
• the amount of the transesterification reaction catalyst used is preferably 0.00001% by mass or more and 0.1% by mass or less, more preferably 0.0001% by mass or more and 0.05% by mass or less, relative to the total mass of the raw materials.
• the transesterification catalyst used in the transesterification reaction is not consumed in the transesterification reaction when heat treatment is performed following the production of polycarbonate diol, so it can be calculated based on the amount of the transesterification reaction catalyst used.
• the metal amount of the transesterification reaction catalyst contained in the polycarbonate diol is determined by measuring by ICP (inductively coupled plasma).
• the polycarbonate diol (I-1) used in the production of the polycarbonate diol composition of the present embodiment is added with a catalyst poison such as a phosphate ester compound in order to deactivate the transesterification reaction catalyst used in the production thereof. There may be.
• polycarbonate diol (I-1) which is a raw material, contains a catalyst poison or the like of the transesterification catalyst used during its production, it is usually treated with ether diol (II-1) or ester diol (IV-1 ) and the polycarbonate diol (I-1) tend to be difficult to proceed with. Therefore, when producing the polycarbonate diol composition of the present embodiment, a necessary amount of the transesterification reaction catalyst described above can be newly added.
• the transesterification reaction in the present embodiment tends to proceed easily.
• a necessary amount of the transesterification reaction catalyst can be newly added. In that case, the same transesterification catalyst as used in the production of the starting material polycarbonate diol (I-1) can be employed.
• the polycarbonate diol (I-1) used for producing the polycarbonate diol composition of the present embodiment may be a homopolycarbonate diol obtained from one type of diol compound, or a copolymer obtained from two or more types of diol compounds. A polycarbonate diol may also be used.
• a polycarbonate diol composition can be obtained by transesterification using any of the polycarbonate diols (I-1) exemplified above.
• homopolycarbonate diols obtained using 1,6-hexanediol which is widely used in the market, are usually solid at room temperature. Therefore, the polycarbonate diol composition obtained by the transesterification reaction with the homopolycarbonate diol also tends to be solid at room temperature.
• a copolymer polycarbonate diol obtained using any two of 1,4-butanediol, 1,5-pentanediol and 1,6-hexanediol is liquid at room temperature. Therefore, the polycarbonate diol composition obtained by the transesterification reaction with the copolymerized polycarbonate diol also tends to be liquid at room temperature.
• n11 represents the repeating number of the carbonate structure (-R 111 -O-CO-O-). Although n11 is an arbitrary integer, the average value of n11 is preferably in the range of 1 to 50, more preferably in the range of 2 to 50, still more preferably in the range of 3 to 30, and in the range of 4 to 20. is particularly preferred.
• the number average molecular weight of the polycarbonate diol (I-1) used for producing the polycarbonate diol composition of the present embodiment is not particularly limited, but is preferably 500 or more and 5000 or less, more preferably 1000 or more and 3000 or less.
• the number average molecular weight of the polycarbonate diol (I-1) is at least the above lower limit, the performance expected of the polycarbonate diol composition tends to be further improved.
• the number average molecular weight of the polycarbonate diol (I-1) is equal to or less than the above upper limit, it is preferable from the standpoint of handleability during production of the polycarbonate diol composition.
• the ether diol (II-1) used for producing the polycarbonate diol composition of the present embodiment may have a structure represented by the general formula (II-1).
• the ether diol (II-1) is preferably a polyoxyalkylene diol having primary hydroxyl groups at both ends.
• Ether diol (II-1) is commercially available as products with various molecular weights, and such commercially available products can also be used. Commercially available products of ether diol (II-1) are not particularly limited.
• the number average molecular weight of the ether diol (II-1) is not particularly limited, it is preferably 400 or more and 3000 or less, more preferably 600 or more and 2500 or less.
• the number average molecular weight of the ether diol (II-1) used for production is at least the above lower limit, flexibility tends to be further improved when used in polyurethane, and the number of ether diols (II-1)
• the average molecular weight is equal to or less than the above upper limit, the crystallinity of the polycarbonate diol composition of the present embodiment tends to be further suppressed.
• polycaprolactone diol (III-1) and cyclic ester compound The polycaprolactone diol (III-1) used for producing the polycarbonate diol composition of the present embodiment may have a structure represented by the above general formula (III-1). Among them, polycaprolactone diol (III-1) is commercially available in various molecular weight products, and such commercially available products can also be used. Examples of commercially available products include, but are not particularly limited to, the “PLAXEL” series manufactured by Daicel Organic Synthesis Company, and the “Polylite” series manufactured by DIC Corporation.
• n311 represents the number of repetitions of the structure (--R 311 --O--CO--).
• n311 is an arbitrary integer, but the average value of n311 is 1 or more, preferably 1 or more and 50 or less, more preferably 1 or more and 30 or less, 1 A range of 20 or less is particularly preferable.
• the number average molecular weight of polycaprolactone diol (III-1) is not particularly limited, it is preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less.
• the number average molecular weight of the lactone diol (III-1) used for production is at least the above lower limit, the flexibility of the polyurethane obtained from the polycarbonate diol composition of the present embodiment tends to be further improved, and the lactone diol
• the number average molecular weight of (III-1) is equal to or less than the above upper limit, the polycarbonate diol composition of the present embodiment tends to have a lower viscosity.
• the cyclic ester compound may be subjected to ring-opening polymerization.
• cyclic ester compounds include, but are not limited to, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -C3-C12 such as methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ , ⁇ -dimethyl- ⁇ -caprolactone, 3,3,5-trimethyl ⁇ -caprolactone, and enantholactone (7-heptalidone) cyclic ester compounds of.
• ⁇ -caprolactone which gives the structural unit (III) in which R 31 in the formula (III) is a linear alkylene group having 5 carbon atoms.
• Ester diol (IV-1) used for producing the polycarbonate diol composition of the present embodiment may have a structure represented by general formula (IV-1) above.
• the ester diol (IV-1) is commercially available in various molecular weight products, and such commercially available products can also be used.
• Commercially available products of the ether diol (II-1) are not particularly limited, but examples include the "Polylite” series manufactured by DIC Corporation, the "Kuraray Polyol” series manufactured by Kuraray Co., Ltd., and the "Nipporan” series manufactured by Tosoh Corporation. , "ADEKA New Ace” series manufactured by ADEKA Corporation, and the like.
• n411 represents the number of repetitions of the structure (—CO—R 411 —CO—OR 421 —O—).
• n411 is an arbitrary integer, but the average value of n411 is 1 or more, preferably 1 or more and 50 or less, more preferably 2 or more and 30 or less, and 4 A range of 20 or less is particularly preferable.
• the number average molecular weight of the ester diol (IV-1) is not particularly limited, it is preferably 400 or more and 3000 or less, more preferably 600 or more and 2000 or less.
• the number average molecular weight of the ester diol (IV-1) used for production is at least the above lower limit, the flexibility of the polyurethane obtained from the polycarbonate diol composition of the present embodiment tends to be further improved.
• the number average molecular weight of (IV-1) is equal to or less than the above upper limit, the polycarbonate diol composition of the present embodiment tends to have a lower viscosity.
• the method for producing the polycarbonate diol composition of the present embodiment is not particularly limited, it is selected from the group consisting of polycarbonate diol (I-1), ether diol (II-1), ester diol (IV-1) and cyclic ester compound. It is preferable to manufacture by mixing with at least one kind of compound obtained and stirring while heating.
• the temperature during the reaction is not particularly limited, but is preferably 120°C or higher and 200°C or lower, more preferably 140°C or higher and 180°C or lower.
• the reaction temperature By setting the reaction temperature to the above lower limit or higher, the transesterification reaction can be carried out in a shorter time and tends to be economically efficient.
• the reaction temperature By setting the reaction temperature to the above upper limit or less, there is a tendency that the acid value of the resulting polycarbonate diol composition can be controlled within a specific range, and coloration can be prevented more effectively.
• the oxygen concentration it is preferable to keep the oxygen concentration at 0.5% or less during production.
• the method for reducing the oxygen concentration to 0.5% or less is not particularly limited. After reducing the pressure to s or less, nitrogen substitution is performed and the reaction is performed under a slightly reduced pressure. By setting the oxygen concentration to 0.5% or less, it tends to be possible to suppress the generation of peroxides and prevent the resulting polycarbonate diol composition from being colored.
• nitrogen flow is preferably performed at a nitrogen flow rate of 0.1 L / min or more and 50 L / min or less, and nitrogen flow is performed at 0.2 L / min or more and 30 L / min or less. is more preferable.
• the nitrogen flow rate is at least the above lower limit value, it is possible to prevent contamination of oxygen. It tends to be able to stabilize the hydroxyl value of the product.
• the polycarbonate diol composition of the present embodiment can be used as a raw material for polyurethane to be reacted with polyisocyanate.
• Polyurethanes using the polycarbonate diol composition of the present embodiment are excellent in chemical resistance, heat resistance, and weather resistance. It can be widely used for water-based polyurethane coatings and the like. Furthermore, it can be used for applications such as modifiers for polyesters and polyimides.
• the polyurethane of this embodiment uses the polycarbonate diol composition described above.
• the polyurethane of the present embodiment preferably has a ⁇ M of 1.0 or more and 19.0 or less, and 3.5 or more and 18.5 or less, as calculated by the following formula (B) for the stress at 100% elongation in a tensile test. is more preferably 5.0 or more and 17.0 or less.
• ⁇ M M1-M2 (B) (M1 in formula (B) is the stress at 100% elongation in a tensile test under -20°C conditions, and M2 represents the stress at 100% elongation in a tensile test under 23°C conditions.)
• the polyurethane of this embodiment tends to have an excellent balance between flexibility and durability because ⁇ M is equal to or higher than the above lower limit. Further, since the polyurethane of the present embodiment has a ⁇ M equal to or less than the above upper limit value, the difference in elastic modulus due to temperature is small, so that it tends to be excellent in mechanical properties at low temperatures.
• the method for producing the polyurethane of the present embodiment uses known polyurethane reaction conditions for producing ordinary polyurethanes, and can be carried out in the absence of a solvent or in the presence of a solvent.
• Examples thereof are not particularly limited, but for example, a method of collectively mixing the above-described polycarbonate diol composition, other polyols, polyisocyanate and chain extender to react (hereinafter sometimes referred to as “one-shot method”). ), or a method in which the above-described polycarbonate diol composition, other polyols and polyisocyanate are first reacted to prepare a prepolymer having both terminal isocyanate groups, and then the prepolymer and a chain extender are reacted (hereinafter referred to as "prepolymer (sometimes referred to as "law”), etc.
• prepolymer sometimes referred to as "law”
• the isocyanate compound contained in the polyurethane of the present embodiment is not particularly limited as long as it functions as a curing agent, and one having two or more isocyanate groups at the end is used.
• isocyanate compounds include, but are not limited to, chain aliphatic diisocyanates, cycloaliphatic diisocyanates, aromatic diisocyanates, and isocyanate compounds having three or more isocyanate groups, and these isocyanate compounds. Examples include isocyanurate-modified products and biuret-modified products.
• the chain aliphatic diisocyanate is not particularly limited, but includes, for example, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.
• the cycloaliphatic diisocyanate is not particularly limited, but examples include isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1-methyl-2,4-cyclohexane diisocyanate, 1-methyl-2,6-cyclohexane diisocyanate, 4,4' -dicyclohexylmethane diisocyanate and the like.
• the aromatic diisocyanate is not particularly limited, but includes, for example, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate (hereinafter sometimes abbreviated as "MDI"), xylylene diisocyanate and naphthylene diisocyanate.
• MDI 4,4'-diphenylmethane diisocyanate
• the isocyanate compound having 3 or more isocyanate groups is not particularly limited, but examples include triphenylmethane-4,4′-4′′-triisocyanate, 1,3,5-triisocyanatobenzene, 2,4 ,6-triisocyanatotoene and 4,4'-dimethyldiphenylmethane-2,2',5,5'-tetraisocyanate.
• a commercially available isocyanate compound may be used, or it may be synthesized using a known method.
• the content of the isocyanate compound may be appropriately adjusted according to the molar amount of hydroxyl groups in the polyol that is the main ingredient.
• the molar ratio (NCO/OH) of the isocyanate groups of the isocyanate compound to the hydroxyl groups of the polycarbonate diol can be, for example, 0.2 or more and 5.0 or less, for example, 0.4 or more and 3.0. For example, it can be 0.5 or more and 2.0 or less.
• the NCO/OH ratio is at least the above lower limit, a tougher coating film tends to be obtained.
• the NCO/OH is equal to or less than the above upper limit, the smoothness of the coating film tends to be further improved.
• chain extender used in producing the polyurethane of the present embodiment is not particularly limited, but examples include ordinary polyols and polyamines.
• polyol is not particularly limited, examples thereof include linear diols, branched diols, cyclic diols, diols having aromatic rings, and the like.
• linear diols include, but are not limited to, ethylene glycol, 1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8-octane. diol, 1,9-nanonediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol and the like.
• branched diols include, but are not limited to, 2-methyl-1,8-octanediol, neopentyl glycol, 2-ethyl-1,6-hexanediol, 2-methyl-1,3-propanediol. , 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol and the like.
• the cyclic diol is not particularly limited, but includes, for example, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 2-bis(4-hydroxycyclohexyl)-propane and the like.
• the diol having an aromatic ring is not particularly limited, but examples include p-xylenediol, p-tetrachloroxylenediol, 1,4-bis(hydroxyethoxy)benzene, 2,2-bis[(4-hydroxyethoxy) phenyl]propane and the like.
• Polyamines are not particularly limited, but include, for example, hydroxylamines and polyamines.
• hydroxylamines include, but are not limited to, N-methylethanolamine, N-ethylethanolamine, and the like.
• polyamines include, but are not limited to, ethylenediamine, 1,3-diaminopropane, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 2-hydroxyethylpropylenediamine, Di-2-hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, 2-hydroxypropylethylenediamine, di-2-hydroxypropylethylenediamine, 4,4'-diphenylmethanediamine, methylenebis(o-chloroaniline), xylylenediamine , diphenyldiamine, tolylenediamine, hydrazine, piperazine, N,N'-diaminopiperazine and the like.
• chain extenders may be used alone or in combination of two or more.
• the synthetic leather of this embodiment contains the polyurethane described above.
• the synthetic leather of the present embodiment is not particularly limited, but examples thereof include synthetic leather in which a base fabric, an adhesive layer, an intermediate layer and a skin layer are sequentially laminated.
• at least one selected from the group consisting of the base fabric, the adhesive layer, the intermediate layer and the skin layer preferably contains the polyurethane described above.
• the base fabric various types can be used, and although not particularly limited, examples thereof include fibrous base materials.
• the fibrous base material is not particularly limited, but for example, a fiber assembly in which fibers are shaped into a non-woven fabric, a woven fabric, a net cloth, etc., or a fiber assembly in which each fiber is bonded with an elastic polymer. things, etc.
• the fibers used in this fiber assembly are not particularly limited, but for example, natural fibers such as cotton, hemp, and wool; regenerated or semisynthetic fibers such as rayon and acetate; polyamides, polyesters, polyacrylonitrile, polyvinyl alcohol, and polyolefins. and synthetic fibers such as These fibers may be singly spun fibers or mixed spun fibers.
• Examples of other substrates include, but are not limited to, paper, release paper, plastic films of polyester or polyolefin, metal plates such as aluminum, and glass plates.
• the polyurethane described above for the adhesive layer, intermediate layer, and skin layer.
• a cross-linking agent other resins, antioxidants, ultraviolet absorbers, hydrolysis inhibitors, pigments, dyes, colorants, flame retardants, organic solvents, etc. may be added. can.
• the method for producing the synthetic leather of the present embodiment is not particularly limited as long as the polyurethane described above is used, and a known method for producing synthetic leather can be used.
• paint or coating agent composition The paint or coating agent composition (paint) of the present embodiment uses the polycarbonate diol composition described above.
• a production method known in the industry is used.
• a two-component solvent-based coating composition in which a coating main agent obtained from the polycarbonate diol composition described above and a curing agent composed of polyisocyanate are mixed immediately before coating;
• a one-component solvent-based coating composition comprising a urethane prepolymer having an isocyanate terminal group obtained by:
• a one-component solvent-based coating composition comprising a polyurethane resin obtained by reacting the above polycarbonate diol, an organic polyisocyanate and a chain extender.
• the paint or coating composition (paint) of the present embodiment includes, for example, a curing accelerator (catalyst), a leveling agent, a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a separating
• a curing accelerator catalyst
• a leveling agent such as a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment
• a separating Other additives such as mold agents, fluidity modifiers, plasticizers, antioxidants, UV absorbers, light stabilizers, antifoaming agents, colorants, and solvents can be added.
• a curing accelerator catalyst
• a leveling agent such as a filler, a dispersant, a flame retardant, a dye, an organic or inorganic pigment, a separating
• Other additives such as mold agents, fluidity modifiers, plasticizers, antioxidants, UV absorbers, light stabilizer
• the curing accelerator is not particularly limited, but includes, for example, monoamines, diamines, other triamines, cyclic amines, alcohol amines, ether amines, and metal catalysts that are commonly used.
• Examples of monoamines include, but are not limited to, triethylamine, N,N-dimethylcyclohexylamine, and the like.
• Examples of the diamine include, but are not particularly limited to, tetramethylethylenediamine.
• the alcohol aminon is not particularly limited, but includes, for example, dimethylethanolamine.
• metal catalysts include, but are not limited to, potassium acetate, potassium 2-ethylhexanoate, calcium acetate, lead octylate, dibutyltin dilaurate, tin octoate, bismuth neodecanoate, bismuth oxycarbonate, bismuth 2 - ethylhexanoate, zinc octoate, zinc neodecanoate, phosphine, phospholine, and the like.
• organic solvents include, but are not limited to, amide solvents, sulfoxide solvents, ketone solvents, ether solvents, ester solvents, carbonate solvents, aromatic hydrocarbon solvents, and the like.
• organic solvents may be used alone or as a mixed solvent of two or more.
• hydroxyl value of the polycarbonate diol (composition) was measured by the following method. First, using a volumetric flask, pyridine was added to 12.5 g of acetic anhydride to make 50 mL to prepare an acetylation reagent. Next, 2.5 g of the sample was accurately weighed into a 100 mL eggplant flask. Next, 5 mL of the acetylating reagent and 10 mL of toluene were added to the round-bottomed flask using a whole pipette, and a cooling tube was attached to stir and heat the solution in the round-bottomed flask at 100° C. for 1 hour.
• x is the repeating structural unit represented by the general formula (I) with respect to the total mass (% by mass) of the repeating structural units represented by the general formulas (I) to (IV) is the content (% by mass) of the polycarbonate diol composition
• y is the titration amount (mL) of the polycarbonate diol composition by the turbidity point titration method
• Mn is the number average molecular weight of the polycarbonate diol composition.
• Molecular weight (B) A portion of the polyurethane film obtained in Application Examples and Comparative Application Examples described later was cut out, and an N,N-dimethylformamide solution was prepared so that the concentration of polyurethane was 0.1% by mass. manufactured by HLC-8320 (column: Tskgel SuperHM-H, 4 columns), and a solution of 2.6 g of lithium bromide dissolved in 1 L of dimethylformamide is used as the eluent. The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polyurethane were measured. Also, the molecular weight distribution (Mw/Mn) was calculated from these measurement results.
• Turbidity point titration 0.5 x I x 56.1/(J x K) (iii)
• I represents the titration amount (mL) obtained above
• J represents the weighed sample mass (g)
• K represents the hydroxyl value of the polycarbonate diol composition (mg-KOH/g ).
• Acid value The acid value of the polycarbonate diol compositions obtained in Examples and Comparative Examples described later was measured according to JIS K 0070-1992 except that the solvent was changed to toluene/ethanol (2/1). asked.
• GC analysis uses gas chromatography GC-14B (manufactured by Shimadzu Corporation, Japan) equipped with DB-WAX (manufactured by J&W, USA) as a column, diethylene glycol diethyl ester as an internal standard, flame ionization type detection group (FID ) was used as a detector to quantitatively analyze each component.
• the temperature rise profile of the column was as follows: after holding at 60°C for 5 minutes, the temperature was raised to 250°C at 10°C/min.
• the composition of the polycarbonate diol composition was obtained from each alcohol component and the dibasic acid-derived methyl ester component detected from the above analysis results.
• the composition of polyester polycarbonate polyol containing dibasic acid is obtained by subtracting the same number of moles of diol from the number of moles of methyl ester derived from dibasic acid. , the number of moles of the diols constituting the carbonate skeleton was determined (when multiple diols were used, the ratio of the diols determined by gas chromatography was used to determine the composition of the diol in the carbonate skeleton and the composition of the diol in the ester skeleton. are the same).
• ⁇ 100% elongation stress (hereinafter sometimes referred to as “ ⁇ M”) From the 100% modulus (stress at 100% elongation) obtained in [Evaluation 1] and [Evaluation 2] above, ⁇ M was obtained by the following formula (B).
• ⁇ M M1-M2 (B) (M1 in formula (B) is the stress at 100% elongation under the -20°C condition obtained in [Evaluation 2], and M2 is the stress at 100% elongation under the 23°C condition obtained in [Evaluation 1]. be.)
• A-1 Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000” (trade name), number average molecular weight: about 2000, in general formula (II-1), R 211 : tetramethylene group, n211: about 28)
• A-2 Polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG1000” (trade name), number average molecular weight: about 1000, in general formula (II-1), R 211 : tetramethylene group, n211: about 14)
• A-3 Polyoxyethylene polyoxypropylene glycol (manufactured by Sanyo Chemical Industries, Ltd., "Newpol PE-61” (trade name), number average molecular weight: about 2000, R 211 in general formula (II-1): isopropylene group and methylene group, n211: about 35)
• A-4 Polyoxyethylene polyoxypropylene glycol (manufactured by
• the reactor was directly connected to a condenser, the temperature of the oil bath was raised to 180° C., the pressure was gradually lowered, and the reaction was continued for another 3 hours to produce polycarbonate diol P-1 (466 g), which is liquid at room temperature. Obtained.
• the hydroxyl value of the obtained polycarbonate diol P-1 was 55.2 mg-KOH/g.
• the polycarbonate diol P-1 thus obtained had a number average molecular weight of 2,033.
• the reactor was directly connected to a condenser, the temperature of the oil bath was raised to 180° C., and the pressure was gradually lowered to carry out the reaction for another 8 hours to obtain polycarbonate diol P-2 (462 g), which is liquid at room temperature. Obtained.
• the obtained polycarbonate diol P-2 had a hydroxyl value of 56.1 mg-KOH/g.
• the polycarbonate diol P-2 thus obtained had a number average molecular weight of 2,000.
• polycarbonate diol P-3 (478 g), which is liquid at room temperature. Obtained.
• the obtained polycarbonate diol P-3 had a hydroxyl value of 112.0 mg-KOH/g.
• the polycarbonate diol P-3 thus obtained had a number average molecular weight of 1,002.
• Example 1 Production of polycarbonate diol composition SA-1 90 mass of polycarbonate diol P-2 obtained in Synthesis Example 2 was placed in a 1 L glass flask (hereinafter also referred to as "reactor") equipped with a stirrer. (360 g) and 10 parts by mass (40 g) of polyoxytetramethylene glycol (manufactured by Mitsubishi Chemical Corporation, "PTMG2000” (trade name), number average molecular weight: about 2000). Then, in the reactor, 0.1 kPa. After the pressure was reduced to 120° C. for 10 minutes, the mixture was purged with nitrogen, and it was confirmed that the oxygen concentration was 0.5% or less.
• reactor 1 L glass flask
• the reactor While maintaining a nitrogen flow rate of 1 L/min, the reactor was heated and stirred at a temperature of about 145° C. for 12 hours. The reaction solution was subjected to turbidity point titration over time, and when it was confirmed that there was no change in the turbidity point titration amount, dibutyl phosphate was added to titanium tetra-n-butoxide so that the mass ratio was 1.3 times. Then, the mixture was heat-treated for 3 hours at 110° C. as the internal temperature of the reactor to obtain a polycarbonate diol composition SA-1. Each physical property of the resulting polycarbonate diol composition SA-1 was measured by the methods described above. Table 1 shows the results.
• the hydroxyl value of the resulting polycarbonate diol composition SA-1 was 56.6 mg-KOH/g.
• the polycarbonate diol composition SA-1 thus obtained had a number average molecular weight of 1,982.
• the obtained polycarbonate diol composition SA-1 contained a repeating structural unit represented by the following formula (A1) and a repeating structural unit represented by the following formula (B1).
• A1 In general formula (A1), R 11 is an aliphatic hydrocarbon group having 4 or 6 carbon atoms.)
• ... (B1) In general formula (B1), R 21 is a tetramethylene group, and the average value of n21 is about 28.)
• Examples 2 to 13 The reaction was carried out under the same conditions and by the same method as in Example 1, except that the types and amounts of each raw material were changed as shown in Tables 1 and 2, respectively, to obtain polycarbonate diol compositions SA- of Examples 2 to 13. 2 to SA-13 were obtained. Periodical quantification and physical properties during turbidity point titration of the obtained polycarbonate diol compositions SA-2 to SA-13 were measured by the above methods. Results are shown in Tables 1 and 2. In addition, the obtained polycarbonate diol compositions SA-2 to SA-13 were sequentially represented by repeating structural units represented by the following formulas (A2) to (A13) and the following formulas (B2) to (B13). and a repeating structural unit. ...
• the polyurethanes obtained from the polycarbonate diol compositions of Examples are excellent in flexibility and mechanical properties at low temperatures, and are also excellent in balance with durability such as resistance to moist heat. all right.
• the APHA of the polyurethane solution obtained from the polycarbonate diol composition of the example also changed well with time.
• the polycarbonate diol composition of the present embodiment can be made high-solid during the production of paints and polyurethanes, and is useful as a raw material for paints and polycarbonate-based polyurethanes.
• the polyurethane produced using the polycarbonate diol composition of the present embodiment has a stable color tone, excellent low-temperature flexibility, and excellent durability. It can be suitably used in a wide range of fields such as paints and high-performance elastomers.

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