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EP-4047034-B1 - POLYCARBONATE DIOL COMPOSITION

EP4047034B1EP 4047034 B1EP4047034 B1EP 4047034B1EP-4047034-B1

Inventors

  • HOSHINO, ERIKO
  • KAWAI, YASUFUMI
  • MASUBUCHI, TETSUO

Dates

Publication Date
20260506
Application Date
20201015

Claims (9)

  1. A polycarbonate diol composition comprising a polycarbonate diol having a structure represented by the following general formula (I) and a polycarbonate structure represented by the following general formula (II), wherein a melt viscosity at 50°C, measured as described in in the description, is 1000 to 10000 mPa·s, and an average value of the number of repeats represented by n11 in the following general formula (I) is 12 or larger, wherein n11 is determined as described in the description: wherein R 11 is a divalent linear, branched or cyclic aliphatic, or aromatic hydrocarbon group having 2 or more and 20 or less carbon atoms, and a plurality of R 11 moieties are the same as or different from each other; and n11 is an arbitrary integer, wherein R 21 is a divalent linear, branched or cyclic aliphatic, or aromatic hydrocarbon group having 2 or more and 15 or less carbon atoms, and a plurality of R 21 moieties are the same as or different from each other; and n21 is an arbitrary integer, wherein a structure of the general formula (I) wherein R 11 is a divalent linear and/or branched aliphatic hydrocarbon group having 3 carbon atoms constitutes 60% by mass or more and 95% by mass or less of the structure represented by the general formula (I), and the content of this structure is determined as described in the description, provided that the polycarbonate polyols of Polymerization Example 19 and Polymerization Example 20 of EP4026863 A1 are excluded.
  2. The polycarbonate diol composition according to claim 1, wherein the average value of the number of repeats represented by n11 in the general formula (I) is 15 or larger.
  3. The polycarbonate diol composition according to claim 1 or 2, wherein at least a portion of the polycarbonate diol has a structure of the general formula (II) wherein R 21 is at least two or more selected from the group consisting of divalent linear and branched aliphatic hydrocarbon groups having 2 or more and 15 or less carbon atoms.
  4. The polycarbonate diol composition according to any one of claims 1 to 3, wherein based on the total mass of the structure represented by the general formula (I) and the polycarbonate structure represented by the general formula (II), a content of the structure represented by the general formula (I) is 5% by mass or more and 40% by mass or less, and a content of the polycarbonate structure represented by the general formula (II) is 60% by mass or more and 95% by mass or less.
  5. The polycarbonate diol composition according to any one of claims 1 to 4, wherein a glass transition temperature measured with a differential scanning calorimeter as described in "[Physical property 5] Measurement of glass transition temperature (Tg)" in the description, is -50°C or lower.
  6. The polycarbonate diol composition according to any one of claims 1 to 5, wherein state at 23°C, determined as described in "[Physical property 6] Confirmation of State of polycarbonate diol composition" in the description, is liquid and transparent.
  7. The polycarbonate diol composition according to any one of claims 1 to 6, wherein an area ratio (%) of a number-average molecular weight (Mn) of 1000 or lower in molecular weight calculation results of the polycarbonate diol composition obtained by calculation by gel permeation chromatography as described in "[Physical property 3] Number-average molecular weight (B)" in the description, is 7% or less.
  8. A polyurethane prepared using the polycarbonate diol composition according to any one of claims 1 to 7.
  9. A synthetic leather comprising a base fabric, an adhesive layer, an intermediate layer and a surface skin layer laminated in order, the synthetic leather comprising the polyurethane according to claim 8.

Description

Technical Field The present invention relates to a polycarbonate diol composition, a polyurethane and a synthetic leather. Background Art Polyurethane resins have heretofore been used in a wide range of fields such as synthetic leather, artificial leather, adhesives, coating materials for furniture, and coating materials for automobiles. Of raw materials of the polyurethane resins, polyether, polyester, and polycarbonate are used as polyol components to be reacted with isocyanate. However, in recent years, there has been a growing demand for the resistance, such as heat resistance, weather resistance, hydrolysis resistance, solvent resistance, sunscreen resistance, or scratch resistance, of polyurethane resins. According to Non Patent Document 1, in general, polyether polyol as a polyol component has low viscosity. Hence, polyurethane obtained using polyether polyol is reportedly excellent in flexibility and hydrolysis resistance but inferior in heat resistance or weather resistance. Polyurethane obtained using polyester polyol is inferior in hydrolysis resistance, though heat resistance and weather resistance are improved. By contrast, polyurethane obtained using polycarbonate polyol has the best tough grade in terms of durability such as heat resistance, chemical resistance, and hydrolysis resistance. For example, Patent Document 1 discloses a method for producing copolymerized polycarbonate diol economically and conveniently. For example, Patent Document 2 discloses a polycarbonate diol/polyether block copolymer. List of Prior Art Documents Patent Document Patent Document 1: Japanese Patent Laid-Open No. 3-252420Patent Document 2: Japanese Patent Laid-Open No. 2006-124486 Non Patent Document Non Patent Document 1: "Case Studies of Polyurethane Material Selection, Structure Control and Modification" published by Technical Information Institute Co., Ltd., 1st edition issued in December 2014, pp. 51-62 EP 4026863 A1, published after the application date of the present application, discloses polycarbonate polyol compositions comprising reaction products of a polycarbonate polyol and polyoxypropylene glycol. WO 2019131617 and JP 2014 080530 A disclose a polycarbonate diol compositions comprising reaction products of polycarbonate diols and polyethylene glycol. EP 2736974 A2 discloses a poly(ethylene carbonate) polyol initiated with a polypropylene oxide capped with polyethylene oxide. EP 0216106 A2 discloses a polytetramethylene oxide diol having diphenol carbonate end groups of bisphenol A. Summary of Invention Problems to be Solved by Invention However, polycarbonate polyol has high viscosity and requires a large amount of a solvent for the production of coating materials or polyurethane. A polyurethane resin obtained using polycarbonate diol described in Patent Document 1 or 2 is susceptible to improvement for purposes that require strict physical properties of low-temperature flexibility and durability. Accordingly, the present invention has been made in light of the situation described above, and an object of the present invention is to provide a polycarbonate diol composition that is capable of reducing the amount of a solvent used at the time of coating material or polyurethane production, can produce polyurethane excellent in low-temperature flexibility and also excellent in oleic acid resistance and moist heat resistance, and can produce a coating material composition excellent in film formability even if a solid content concentration is high. Means for Solving Problems The present inventor has conducted diligent studies and consequently completed the present invention by finding that a polycarbonate diol composition that contains a polycarbonate diol having a specific structure and has a melt viscosity in a specific range at 50°C is capable of reducing the amount of a solvent used at the time of coating material or polyurethane production, can produce polyurethane excellent in low-temperature flexibility and also excellent in oleic acid resistance and moist heat resistance, and can produce a coating material composition excellent in film formability even if a solid content concentration is high. Specifically, the present invention includes the aspects described by the claims. Advantages of Invention The polycarbonate diol composition of the present invention is capable of reducing the amount of a solvent used at the time of coating material or polyurethane production, can produce polyurethane excellent in low-temperature flexibility and also excellent in oleic acid resistance and moist heat resistance, and can produce a coating material composition excellent in film formability even if a solid content concentration is high. Mode for Carrying Out Invention Hereinafter, the mode for carrying out the present invention (hereinafter, referred to as the "present embodiment") will be described in detail. The present invention is not limited by the description below and can be carried out with various modif