US-12624151-B2 - Polycarbonate polyol composition

Abstract

Provided is a polycarbonate polyol composition including an unmodified polycarbonate polyol having a carbonate structure represented by the following formula (A), and a modified polycarbonate polyol having a carbonate structure represented by the following formula (A) and a urethane structure represented by the following formula (B), wherein 90% by mol or more of the total quantity of terminal groups of all the compounds in the composition is hydroxy groups, and the number of functional groups calculated according to the following expression (II) is 2.00 to 10.00: The number of functional groups=Mn×OHV/56.11/1000  (II)

Inventors

• Yasufumi KAWAI

Assignees

• ASAHI KASEI KABUSHIKI KAISHA

Dates

Publication Date

20260512

Application Date

20211001

Priority Date

20201009

Claims (18)

1. 1 . A polycarbonate polyol composition comprising an unmodified polycarbonate polyol having a carbonate structure represented by the following formula (A), and a modified polycarbonate polyol having a carbonate structure represented by the following formula (A) and a urethane structure represented by the following formula (B), wherein 90% by mol or more of the total quantity of terminal groups of all the compounds in the composition is hydroxy groups, and the number of functional groups calculated according to the following expression (II) is 2.20 to 10.00; and wherein in infrared absorption spectrum absorbance measured by FT-IR, when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 1691 cm −1 from the urethane structure represented by the formula (B) is defined as PB and when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 3000 to 3800 cm −1 from a hydroxy group is defined as POH, a value of PB/POH is 1.00 to 3.50: wherein R represents a divalent linear, branched or cyclic aliphatic hydrocarbon group optionally containing a heteroatom, or a divalent aromatic hydrocarbon group optionally containing a heteroatom, the number of functional groups=Mn×OHV/56.11/1000 (II) wherein Mn represents a number-average molecular weight of the polycarbonate polyol composition determined by GPC measurement, and OHV represents a hydroxy value of the polycarbonate polyol composition, and wherein in infrared absorption spectrum absorbance measured by FT-IR, when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 1743 cm −1 from the carbonate structure represented by the formula (A) is defined as PA and when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 1691 cm −1 from the urethane structure represented by the formula (B) is defined as PB, a value of PB/PA is 0.05 to 1.00.
2. 2 . The polycarbonate polyol composition according to claim 1 , wherein the hydroxy value is 5 to 700 mg-KOH/g.
3. 3 . The polycarbonate polyol composition according to claim 1 , wherein APHA, measured in accordance with JIS K 0071-1, is 100 or less.
4. 4 . The polycarbonate polyol composition according to claim 1 , wherein in infrared absorption spectrum absorbance measured by FT-IR, when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 1743 cm −1 from the carbonate structure represented by the formula (A) is defined as PA and when a height of an infrared absorption spectrum absorbance (Abs) peak around a wavenumber of 1691 cm −1 from the urethane structure represented by the formula (B) is defined as PB, a value of PB/PA is 0.05 to 1.00.
5. 5 . The polycarbonate polyol composition according to claim 1 , wherein the modified polycarbonate polyol comprises a cyclic structure.
6. 6 . The polycarbonate polyol composition according to claim 5 , wherein the cyclic structure is an isocyanurate ring.
7. 7 . The polycarbonate polyol composition according to claim 1 , wherein the unmodified polycarbonate polyol and/or the modified polycarbonate polyol comprises a hydrophilic structure.
8. 8 . The polycarbonate polyol composition according to claim 7 , wherein the hydrophilic structure is a nonionic hydrophilic group.
9. 9 . The polycarbonate polyol composition according to claim 7 , wherein the hydrophilic structure is an anionic hydrophilic group.
10. 10 . The polycarbonate polyol composition according to claim 7 , wherein the composition is capable of being dispersed in water.
11. 11 . A coating material comprising the polycarbonate polyol composition according to claim 1 .
12. 12 . A coating agent comprising the polycarbonate polyol composition according to claim 1 .
13. 13 . A polyurethane obtained using the polycarbonate polyol composition according to claim 1 .
14. 14 . An artificial leather obtained using the polyurethane according to claim 13 .
15. 15 . A synthetic leather obtained using the polyurethane according to claim 13 .
16. 16 . A coating material obtained using the polyurethane according to claim 13 .
17. 17 . A coating agent obtained using the polyurethane according to claim 13 .
18. 18 . An aqueous polyurethane obtained using the polycarbonate polyol composition according to claim 1 .

Description

TECHNICAL FIELD The present invention relates to a polycarbonate polyol composition. 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 starting 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. In general, a polyurethane resin obtained using polycarbonate polyol as a polyol component is known to be superior in moist heat resistance, solvent resistance, sunscreen resistance, scratch resistance, etc. to a polyurethane resin obtained using polyether or polyester. For example, Patent Document 1 discloses a polycarbonate polyol obtained using 1,5-pentanediol and 1,6-hexanediol as diol components. For example, Patent Document 2 discloses a polycarbonate polyol obtained using 1,4-butanediol and 1,6-hexanediol. For example, Patent Document 3 discloses an ultraviolet absorber-resistant polyurethane composition comprising a polyisocyanate (A), an amino alcohol (B), and a polyol (C) as monomer units, and comprising a hydroxy group-terminated prepolymer having an isocyanurate ring structure, and a curing agent. For example, Patent Document 4 discloses a leather-like sheet comprising a skin layer (C), an adhesive layer (D), and a support layer (E), the skin layer (C) being formed using a urethane resin composition containing a urethane resin (A) having two or more hydroxy groups at least one end, and an aqueous medium (B). LIST OF PRIOR ART DOCUMENTS Patent Document Patent Document 1: International Publication No. WO 2001/090213Patent Document 2: International Publication No. WO 2009/063767Patent Document 3: Japanese Patent Laid-Open No. 2017-048320Patent Document 4: International Publication No. WO 2013/027489 SUMMARY OF INVENTION Problems to be Solved by Invention However, for example, a coating material composition obtained using a polycarbonate polyol as a polyol component requires a more time for drying than that of a coating material composition obtained using polyether or polyester as a polyol component, and tends to increase a drying step. Also, a polyurethane obtained using a polycarbonate polyol as a polyol component may not meet endurance which has been a requirement expected for polyurethane resins in recent years. Neither Patent Document 1 nor 2 described above mentions the drying properties of a prepared coating material composition. Thus, the techniques disclosed therein are still susceptible to improvement. In general, a polyol having a urethane group is used with an organic solvent having a high solvency, for example, dimethylformamide or methyl ethyl ketone. However, use of the solvents such as carcinogenic dimethylformamide or the deleterious substance methyl ethyl ketone is avoided from the viewpoint of preventing health problems. There is a demand for their substitution by dipropylene glycol monomethyl ether (hereinafter, also abbreviated to “DPM”), etc. which does not correspond to a carcinogen, a toxic substance or a deleterious substance. Neither Patent Document 3 nor 4 described above mentions the solubility of a polycarbonate polyol having a urethane group in DPM, etc. Thus, the techniques disclosed therein are still susceptible to improvement. Accordingly, an object of the present invention is to provide a polycarbonate polyol composition that is excellent in compatibility with DPM and is capable of forming a coating material composition excellent in drying properties and a coating film and/or a polyurethane film excellent in endurance. Means for Solving Problems The present inventor has conducted diligent studies to attain the object and consequently completed the present invention by finding that a polycarbonate polyol composition having a specific structure and specific physical properties is excellent in compatibility with DPM and is capable of forming a coating material composition excellent in drying properties and a coating film and/or a polyurethane film excellent in endurance. Specifically, the present invention is configured as follows. [1] A polycarbonate polyol composition comprising an unmodified polycarbonate polyol having a carbonate structure represented by the following formula (A), and a modified polycarbonate polyol having a carbonate structure represented by the following formula (A) and a urethane structure represented by the following formula (B), wherein 90% by mol or more of the total quantity of terminal groups of all the compounds in the composition is hydroxy groups, andthe number of functional groups calculated according to the following expression (II) is 2.00 to 10.00: wherein R