Polycarbonate diol, polycarbonate diol-containing composition, polycarbonate diol production method, and polyurethane

Abstract

Provided is a polycarbonate polyol used as a raw material of a polyurethane that yields a polyurethane solution having good storage stability and exhibits excellent flexibility and solvent resistance. This polycarbonate polyol is a polycarbonate diol that includes structural units represented by the following Formulae (A) and (B), wherein, R.sup.1 and R.sup.2 each independently represent an alkyl group having 1 to 4 carbon atoms and, in this range of the number of carbon atoms, optionally have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these atoms; and R.sup.3 represents a linear aliphatic hydrocarbon having 3 or 4 carbon atoms. This polycarbonate diol has a molecular weight of 500 to 5,000, and the value of the following Formula (I) is 0.3 to 20.0: (Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%) (I). ##STR00001##

Claims

1. A polycarbonate diol comprising: a structural unit represented by the following Formula (A); and a structural unit represented by the following Formula (B): ##STR00007## wherein, R.sup.1 and R.sup.2 each independently represent an alkyl group having 1 to 4 carbon atoms and, in this range of the number of carbon atoms, optionally have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these atoms; and R.sup.3 represents a linear aliphatic hydrocarbon having 3 or 4 carbon atoms, wherein the polycarbonate diol has a number-average molecular weight of 500 to 5,000, and the value of the following Formula (I) of 0.3 to 20.0:
(Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%)  (I).

2. The polycarbonate diol according to claim 1, wherein the value of the following Formula (I) is 0.5 to 8.0:
(Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%)  (I).

3. The polycarbonate diol according to claim 1, wherein the structural unit represented by Formula (A) is derived from 2,2-dimethyl-1,3-propanediol.

4. The polycarbonate diol according to claim 1, wherein the structural unit represented by Formula (A) is derived from 2-butyl-2-ethyl-1,3-propanediol.

5. The polycarbonate diol according to claim 1, wherein the structural unit represented by Formula (B) is derived from 1,4-butanediol.

6. The polycarbonate diol according to claim 1, wherein a ratio of the number of terminal groups derived from a carbonate compound in the polycarbonate diol is 5.0% by mole or less with respect to the number of all terminal groups.

7. The polycarbonate diol according to claim 1, wherein the amount of the heat of fusion of a melting peak is 0.1 J/g to 10 J/g as measured by a differential scanning calorimeter.

8. A polycarbonate diol-containing composition, comprising a polycarbonate diol that contains a structural unit represented by the following Formula (A) and a structural unit represented by the following Formula (B): ##STR00008## wherein, R.sup.1 and R.sup.2 each independently represent an alkyl group having 1 to 4 carbon atoms and, in this range of the number of carbon atoms, optionally have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these atoms; and R.sup.3 represents a linear aliphatic hydrocarbon having 3 or 4 carbon atoms, wherein the polycarbonate diol has a molecular weight of 500 to 5,000, the value of the following Formula (I) is 0.3 to 20.0:
(Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%)  (I), and wherein the polycarbonate diol-containing composition comprises a hydroxyaryl compound in an amount of 0.1% by weight or less relative to the total weight of the polycarbonate diol-containing composition.

9. The polycarbonate diol-containing composition according to claim 8, comprising at least one metal selected from Groups 1 and 2 of the periodic table.

10. The polycarbonate diol-containing composition according to claim 9, wherein the content of the metal in the polycarbonate diol-containing composition is 100 ppm by weight or less.

11. A method of producing a polycarbonate diol, the method comprising the step of performing a polymerization reaction of at least one carbonate compound (i) selected from the group consisting of dialkyl carbonates, diaryl carbonates and alkylene carbonates, a diol (ii) represented by the following Formula (C), and a diol (iii) represented by the following formula (D) in the presence of a metal compound catalyst: ##STR00009## wherein, R.sup.1 and R.sup.2 each independently represent an alkyl group having 1 to 4 carbon atoms and, in this range of the number of carbon atoms, optionally have an oxygen atom, a sulfur atom, a nitrogen atom, a halogen atom, or a substituent containing these atoms; and R.sup.3 represents a linear aliphatic hydrocarbon having 3 or 4 carbon atoms, wherein the polycarbonate diol has a value of the following Formula (I) of 0.3 to 20.0:
(Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%)  (I).

12. A polyurethane obtainable from the polycarbonate diol according to claim 1.

13. A polyurethane obtainable from the polycarbonate diol-containing composition according to claim 8.

14. An artificial leather or a synthetic leather, obtainable using the polyurethane according to claim 12.

15. A paint or a coating agent, obtained using the polyurethane according to claim 12.

16. A thermosetting elastomer or a thermoplastic elastomer, obtainable using the polyurethane according to claim 12.

17. An aqueous polyurethane paint obtained using the polyurethane according to claim 12.

18. A pressure-sensitive adhesive or an adhesive, obtainable using the polyurethane according to claim 12.

19. An active energy ray-curable polymer composition obtainable using the polycarbonate diol according to claim 1.

Description

EXAMPLES

(1) The present invention will now be described more concretely by way of Examples and Comparative Examples; however, the present invention is not restricted thereto within the gist of the present invention.

(2) [Evaluation Methods]

(3) Polycarbonate diols and polyurethanes obtained in the below-described Examples and Comparative Examples were evaluated by the following methods.

(4) [Evaluation of Polycarbonate Dials]

(5) <Quantification of Content of Terminal Phenoxy Group, Diol, and Phenol>

(6) The subject polycarbonate diol was dissolved in CDCl.sub.3, and 400-MHz .sup.1H-NMR spectroscopy (AL-400, manufactured by JEOL Ltd.) was performed to identify the terminal phenoxy group, a diol(s), and a phenol(s) based on the signal positions of the respective components, after which the content of each component was calculated from integral values. The detection limits in this process were 100 ppm by weight for the weight of a phenol with respect to the weight of the whole sample, and 0.1% by weight for diol compounds such as the compound represented by Formula (A) and the compound represented by Formula (B). The ratio of the terminal phenoxy group was calculated from the ratio between an integral value for one proton of the terminal phenoxy group and an integral value for one proton of a whole terminal, and the detection limit for the terminal phenoxy group was 0.05% with respect to a whole terminal.

(7) <Hydroxyl Value and Number-Average Molecular Weight>

(8) The hydroxyl value of the subject polycarbonate diol was measured by a method using an acetylation reagent in accordance with JIS K1557-1.

(9) Further, from the thus measured hydroxyl value, the number-average molecular weight was determined using the following Formula (II):
Number-average molecular weight=2×56.1/(hydroxyl value×10.sup.−3)  (II)
<Molar Ratios of Structural Unit Derived from Formula (A) and Structural Unit Derived from Formula (B)>

(10) The subject polycarbonate diol was dissolved in CDCl.sub.3, and 400-MHz .sup.1H-NMR spectroscopy (AL-400, manufactured by JEOL Ltd.) was performed to determine the molar ratio of a structural unit derived from Formula (A) and that of a structural unit derived from Formula (B) based on the signal positions of the respective components. The molar ratio between the structural unit derived from Formula (A) and the structural unit derived from Formula (B), the molar ratio of the structural unit derived from Formula (A), and the molar ratio of the structural unit derived from Formula (B) may be hereinafter referred to as “(A)/(B)”, “a” and “b”, respectively.

(11) <Content Ratio of Branched-Chain Moiety in Polymer>

(12) The content ratio of branched-chain moiety in the subject polymer was calculated using the following Formula (III):
(Content ratio of branched-chain moiety in polymer)=(Total molecular weight of R.sup.1and R.sup.2)×(T+1)×a/(Number-average molecular weight of polycarbonate diol)  (III)

(13) In this Formula (III), T represents a total number of the structural units of Formulae (A) and (B) that are contained in the polycarbonate dial, and a represents the molar ratio of the structural unit derived from Formula (A).

(14) The total number (T) of the structural units of Formulae (A) and (B) that are contained in the polycarbonate diol is calculated from the number-average molecular weight of the polycarbonate diol, the molar ratios of the structural unit derived from Formula (A) and the structural unit derived from Formula (B), and the molecular weights of Formula (C) and Formula (D).

(15) <Content Ratio of Carbonate Group in Polymer>

(16) In the same manner as the content ratio of branched-chain moiety in the subject polymer, the content ratio of carbonate group in the polymer of the subject polycarbonate diol was calculated using the following Formula (IV):
(Content ratio of carbonate group in polymer)=(Molecular weight of carbonate group)×T/(Number-average molecular weight of polycarbonate diol)  (IV)
<Value of Formula (I)>

(17) The value of Formula (I) is calculated by: (Content ratio of branched-chain moiety in polymer)/(Content ratio of carbonate group in polymer)×100(%). In other words, from the above, the value of Formula (I) is expressed as follows: Formula (I)={(Total molecular weight of R.sup.1 and R.sup.2)×(T+1)×a/(Number-average molecular weight of polycarbonate diol)}/{(Molecular weight of carbonate group)×T/(Number-average molecular weight of polycarbonate diol)}×100(%).

(18) <Measurement of Melting Peak Temperature and Heat of Fusion>

(19) About 10 mg of the subject polycarbonate diol enclosed in aluminum pan and, using EXSTAR DSC6200 (manufactured by Seiko Instrument, Inc.), an operation of raising and lowering the temperature from 30° C. to 150° C. at a rate of 20° C./min, subsequently from 150° C. to −120° C. at a rate of 40° C./min and then from −120° C. to 120° C. at a rate of 20° C./min was performed in a nitrogen atmosphere. From the thus obtained melting peak, the melting peak temperature and the amount of heat of fusion were determined.

(20) <Catalyst Metal Content in Polycarbonate Diol-Containing Compositions>

(21) About 0.1 g of the subject polycarbonate diol-containing composition was weighed and dissolved in 4 mL of acetonitrile, and 20 mL of pure water was subsequently added thereto so as to allow a polycarbonate diol to precipitate, after which the thus precipitated polycarbonate diol was removed by filtration. The filtered solution was diluted with pure water to a prescribed concentration, and the metal ion concentration was analyzed by ion chromatography. The metal ion concentration of acetonitrile used as a solvent was measured as a blank value, and a value obtained by subtracting the thus measured metal ion concentration of the solvent was defined as the metal content in the polycarbonate diol-containing composition. The measurement conditions were as shown in Table 1 below. Using the analysis results and calibration curves that had been prepared in advance, the concentrations of magnesium, calcium and barium ions were determined.

(22) TABLE-US-00001 TABLE 1 Analysis apparatus “DX-320” manufactured by Nippon Dionex K. K. CHROMATOPAC “C-R7A” manufactured by Shimadzu Corporation Separation column IonPac CS12A Guard column IonPac CG12A Flow rate 1.0 mL/min Injection volume 1.5 mL Pressure 960 to 990 psi Oven temperature 35° C. Detector sensitivity RANGE, 200 μs Suppressor CSRS, current value: 60 mA Eluent 20-mmol/L methanesulfonic acid Retention time Mg: 10.9 min Ca: 13.0 min Ba: 19.4 min
<Content of Hydroxyaryl Compound in Polycarbonate Diol-Containing Composition>

(23) The subject polycarbonate diol was dissolved in CDCl.sub.3, and 400-MHz .sup.1H-NMR spectroscopy (AL-400, manufactured by JEOL Ltd.) was performed to identify a hydroxyaryl compound based on the signal positions of the respective components, and the content of the hydroxyaryl compound was calculated from an integral value. In this process, for example, when the hydroxyaryl compound was phenol, the detection limit was 100 ppm by weight in terms of the weight of phenol with respect to the weight of the whole sample.

(24) [Evaluation Method: Polyurethane]

(25) <Measurement of Isocyanate Group Concentration>

(26) After diluting 20 mL of a di-n-butylamine/toluene (weight ratio: 2/25) mixed solution with 90 mL of acetone, the resultant was titrated with a 0.5 N aqueous hydrochloric acid solution, and the amount of the aqueous hydrochloric acid solution required for neutralization was measured as a blank value. Subsequently, 1 to 2 g of the reaction solution was extracted, and 20 mL of the di-n-butylamine/toluene mixed solution was added thereto, followed by stirring at room temperature for 30 minutes. Thereafter, in the same manner as in the blank measurement, the resultant was diluted with 90 mL of acetone and then titrated with a 0.5 N aqueous hydrochloric acid solution, and the amount of the aqueous hydrochloric acid solution required for neutralization was measured, followed by quantification of the amount of residual amine. From the volume of the aqueous hydrochloric acid solution required for neutralization, the isocyanate group concentration was calculated using the following equations:
Isocyanate group concentration (% by weight)=A×42.02/D

(27) A: Isocyanate groups (mol) contained in sample used for this measurement
A=(B−C)×0.5/1,000×f

(28) B: Amount (mL) of 0.5 N aqueous hydrochloric acid solution required for blank measurement

(29) C: Amount (mL) of 0.5 N aqueous hydrochloric acid solution required for this measurement

(30) f: Titer of aqueous hydrochloric acid solution

(31) D: Sample (g) used for this measurement

(32) <Measurement of Molecular Weight>

(33) As for the molecular weight of the subject polyurethane, a dimethylacetamide solution was prepared such that the concentration of the polyurethane was 0.14% by weight, and the number-average molecular weight (Mn) and the weight-average molecular weight (Mw) were measured in terms of standard polystyrene using a GPC apparatus [manufactured by Tosoh Corporation, trade name: “HLC-8220” (columns: TSKGEL GMH-XL×2)].

(34) <Method of Room-Temperature Tensile Test>

(35) In accordance with JIS K6301, for a polyurethane test piece in the form of a strip having a width of 10 mm, a length of 100 mm and a thickness of about 50 μm, a tensile test was performed using a tensile tester (trade name: “TENSILON UTM-III-100”, manufactured by Orientec Co., Ltd.) at a chuck distance of 50 mm, a tensile rate of 500 mm/min and a temperature of 23° C. (relative humidity: 60%) to measure the stress at 100° elongation and 300° elongation of the test piece as well as the elongation and the stress at break.

(36) <Method of Low-Temperature Tensile Test>

(37) In accordance with JIS K6301, for a polyurethane test piece in the form of a strip having a width of 10 mm, a length of 100 mm and a thickness of about 50 μm, a tensile test was performed at a tensile rate of 500 mm/min using a tensile tester (trade name: “AUTOGRAPH AG-X 5 kN”, manufactured by Shimadzu Corporation) after placing the film in a thermostat bath (trade name: “THERMOSTATIC CHAMBER TCR2W-200T”, manufactured by Shimadzu Corporation) set at −10° C. at a chuck distance of 50 mm and leaving the film to stand at −10° C. for 3 minutes, and the stress was measured at 100% elongation of the test piece.

(38) <Solvent Resistance>

(39) A polyurethane solution was applied onto a fluorocarbon resin sheet (fluorine tape NITOFLON 900, thickness=0.1 mm, manufactured by Nitto Denko Corporation) using a 9.5-mil applicator and sequentially dried under the conditions of at 50° C. for 5 hours, at 100° C. for 0.5 hours, at 100° C. for 0.5 hours in vacuum, and then at 80° C. for 15 hours. Test pieces of 3 cm×3 cm were cut out from the thus obtained polyurethane film and then placed in glass dishes of 10 cmφ in inner diameter containing 50 mL of the respective test solvents. For each test solvent, the weight of the test piece was measured after immersion at the below-described temperature for the below-described time, and the rate of change (%) in the weight of the test piece before and after the immersion (=(Weight of test piece after immersion−Weight of test piece before immersion)/Weight of test piece before immersion×100) was calculated. It is noted here that a weight change rate closer to 0% indicates superior solvent resistance.

(40) Oleic acid resistance: the test piece was immersed in oleic acid at 80° C. for 16 hours.

(41) Ethyl acetate resistance: the test piece was immersed in ethyl acetate at room temperature for 20 minutes.

(42) Ethanol resistance: the test piece was immersed in ethanol at room temperature for 1 hour.

(43) <Storage Stability Test>

(44) The subject polyurethane solution was left to stand in a refrigerator maintained at 10° C., and a change in the polyurethane solution was visually checked at one-week intervals. An evaluation was made as follows based on the period from the initiation of storage to a point at which a change in the polyurethane solution, such as turbidity, was observed.

(45) A change was observed within one month from the initiation of storage: x

(46) A change was observed within three months from the initiation of storage: Δ

(47) A change was observed within six months from the initiation of storage: ∘

(48) No change was observed for six months or longer from the initiation of storage: ⊚

(49) <Production and Evaluation of Polycarbonate Diol>

Example 1-1

(50) To a 5-L glass separable flask equipped with a stirrer, a distillate trap and a pressure adjusting device, 1,167.5 g of 1,4-butanediol (14BD), 86.1 g of neopentyl glycol (NPG), 2,746.4 g of diphenyl carbonate (DPC) and 7.0 mL of an aqueous magnesium acetate tetrahydrate solution (concentration: 8.4 g/L, magnesium acetate tetrahydrate: 59 mg) were added, followed by purging with nitrogen gas. The contents were heat-dissolved by raising the internal temperature to 160° C. with stirring. Subsequently, after the pressure was reduced to 24 kPa over a period of 2 minutes, the reaction was allowed to proceed for 90 minutes while removing phenol out of the system. Then, the reaction was continued while reducing the pressure to 9.3 kPa over a period of 90 minutes and further to 0.7 kPa over a period of 30 minutes, after which the temperature was raised to 170° C. and the reaction was allowed to proceed for another 60 minutes while removing phenol and unreacted diol out of the system, whereby a polycarbonate diol-containing composition was produced. Thereafter, the catalyst was deactivated with an addition of 2.3 mL of a 0.85% aqueous phosphoric acid solution to obtain a polycarbonate diol-containing composition.

(51) The thus obtained polycarbonate diol-containing composition was transferred to a thin-film distillation apparatus at a flow rate of about 20 g/min, and thin-film distillation (temperature: 170° C., pressure: 53 to 67 Pa) was performed. As the thin-film distillation apparatus, a molecular distillation apparatus Model MS-300 manufactured by Sibata Scientific Technology Ltd., which was equipped with an internal condenser having a diameter of 50 mm, a height of 200 mm and an area of 0.0314 m.sup.2 and a jacket, was used.

(52) The results of evaluating the characteristics and physical properties of the polycarbonate diol obtained by this thin-film distillation are shown in Table 2.

(53) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less. Further, with regard to the magnesium content in the polycarbonate diol-containing composition, it is believed that, taking into consideration the production-purification method (thin-film distillation), the added amount (about 10 ppm by weight) remained as it was.

Example 2-1

(54) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 926.9 g of 1,4-butanediol (14BD), 13.0 g of neopentyl glycol (NPG), 2,060.1 g of diphenyl carbonate (DPC), and 5.3 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(55) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Example 3-1

(56) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 908.2 g of 1,4-butanediol (14BD), 26.9 g of neopentyl glycol (NPG), 2,064.9 g of diphenyl carbonate (DPC), and 5.3 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(57) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Example 4-1

(58) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 831.5 g of 1,4-butanediol (14BD), 118.8 g of neopentyl glycol (NPG), 2,049.7 g of diphenyl carbonate (DPC), and 5.3 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(59) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Example 5-1

(60) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 792.9 g of 1,4-butanediol (14BD), 161.7 g of neopentyl glycol (NPG), 2,045.5 g of diphenyl carbonate (DPC), and 5.3 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(61) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Example 6-1

(62) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 359.5 g of 1,4-butanediol (14BD), 19.8 g of 2-butyl-2-ethyl-1,3-propanediol (BEPD), 820.7 g of diphenyl carbonate (DPC), and 2.1 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(63) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Comparative Example 1-1

(64) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 1,249.2 g of 1,4-butanediol (14BD), 2,750.7 g of diphenyl carbonate (DPC), 7.1 mL of an aqueous magnesium acetate tetrahydrate solution (concentration: 8.4 g/L, magnesium acetate tetrahydrate: 60 mg) and 2.5 mL of a 0.85% aqueous phosphoric acid solution, and the temperature of the thin-film distillation was changed to 200° C. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(65) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Comparative Example 2-1

(66) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 609.7 g of 1,4-butanediol (14BD), 704.6 g of neopentyl glycol (NPG), 2,685.7 g of diphenyl carbonate (DPC), 6.9 mL of an aqueous magnesium acetate tetrahydrate solution (concentration: 8.4 g/L, magnesium acetate tetrahydrate: 58 mg) and 2.4 mL of a 0.85% aqueous phosphoric acid solution, and the temperature of the thin-film distillation was changed to 200° C. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(67) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Comparative Example 3-1

(68) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 1,224.4 g of 1,6-hexanediol (16HD), 81.2 g of neopentyl glycol (NPC), 2,194.3 g of diphenyl carbonate (DPC), and 5.7 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(69) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

Comparative Example 4-1

(70) A polycarbonate diol was obtained in the same manner as in Example 1-1 except that, in the production of the polycarbonate diol, the raw materials were changed to 273.5 g of 1,4-butanediol (14BD), 145.3 g of 2-butyl-2-ethyl-1,3-propanediol (BEPD), 781.3 g of diphenyl carbonate (DPC), and 2.0 mL of an aqueous magnesium acetate tetrahydrate solution. The results of evaluating the characteristics and physical properties of the thus obtained polycarbonate diol are shown in Table 2.

(71) The thus obtained polycarbonate diol-containing composition had a hydroxyaryl compound content of 100 ppm by weight or less.

(72) TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Example Comparative Comparative Comparative Comparative 1-1 2-1 3-1 4-1 5-1 6-1 Example 1-1 Example 2-1 Example 3-1 Example 4-1 Formulation NPG/ NPG/ NPG/ NPG/ NPG/ BEPD/ 14BD NPG/ NPG/ BEPD/ 14BD 14BD 14BD 14BD 14BD 14BG 14BD 16HD 14BD Property white white white white white white white solid viscous white solid viscous solid solid solid solid solid solid liquid liquid Hydroxyl value 54.0 51.2 54.1 52.6 50.7 54.8 55.7 53.9 51.5 61.2 (mg-KOH/g) Number-average 2,078 2,191 2,074 2,133 2,213 2,047 2,014 2,082 2,179 1,833 molecular weight Mn (A)/(B) 6/94 1/99 3/97 10/90 15/85 3/97 0/100 45/55 7/93 22/78 Terminal not not not not not not not detected not detected not detected not detected phenoxy group detected detected detected detected detected detected Formula (I) 3.2 0.5 1.6 5.3 7.9 4.6 0.0 23.9 3.8 33.8 Amount of heat 3.8 55.5 15.5 peak not peak not 65.5 39.2 peak not 37.3 peak not of fusion (J/g) detected detected detected detected
[Production and Evaluation of Polyurethanes]

Example 1-2

(73) To a separable flask equipped with a thermocouple and a condenser tube, 98.5 g of the polycarbonate diol produced in Example 1-1, which had been heated to 80° C. in advance, was added, and the separable flask was immersed in a 60° C. oil bath. Subsequently, 25.4 g of 4,4′-dicyclohexylmethane diisocyanate (hereinafter, referred to as “H12MDI”, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.4 g of triisooctyl phosphite (hereinafter, referred to as “TiOP”, manufactured by Tokyo Chemical Industry Co., Ltd.) were further added, and the inside of the flask was heated to 80° C. for about 1 hour with stirring at 60 rpm in a nitrogen atmosphere. Thereafter, 9.4 mg of NEOSTANN U-830 (hereinafter, referred to as “U-830”, manufactured by Nitto Kasei Co., Ltd.) was added as an urethanization catalyst and, once heat generation subsided, the oil bath was heated to 100° C., followed by further stirring for about 4 hours. The concentration of isocyanate groups was analyzed and consumption of a theoretical amount of isocyanate groups was confirmed to obtain a prepolymer (hereinafter, may be abbreviated as “PP”). Then, 111.8 g of the thus obtained PP was diluted with 13.3 g of dehydrated toluene (manufactured by Wako Pure Chemical Industries, Ltd.). Subsequently, 256.6 g of dehydrated N,N-dimethylformamide (hereinafter, referred to as “DMF”; manufactured by Wako Pure Chemical Industries, Ltd.) was added, the flask was immersed in a 55° C. oil bath, and the PP was dissolved with stirring at about 200 rpm. After analyzing the concentration of isocyanate groups in the resulting prepolymer solution, the flask was immersed in an oil bath set at 35° C., and isophorone diamine (hereinafter, referred to as “IPDA”; manufactured by Tokyo Chemical Industry Co., Ltd.) in a required amount calculated from the residual isocyanate, which was 6.6 g, was added in parts with stirring at 150 rpm. After about 1 hour of stirring, 0.5 g of morpholine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the resultant was further stirred for 1 hour to obtain a polyurethane solution. This polyurethane solution was applied onto a polyethylene film at a uniform thickness using a doctor blade and subsequently dried using a dryer, whereby a polyurethane film was obtained. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Example 2-2

(74) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate diol produced in Example 2-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Example 3-2

(75) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate dial produced in Example 3-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Example 4-2

(76) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate diol produced in Example 4-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Example 5-2

(77) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate dial produced in Example 5-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Comparative Example 1-2

(78) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the raw materials were changed to 90.3 g of the polycarbonate diol produced in Comparative Example 1-1, 23.8 g of H12MDI, 0.3 g of TiOP, 8.5 mg of U-830, 105.2 g of PP, 11.8 g of dehydrated toluene, 243.9 g of DMF, 6.3 g of IPDA, and 0.5 g of morpholine. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Comparative Example 2-2

(79) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the raw materials were changed to 90.4 g of the polycarbonate diol produced in Comparative Example 2-1, 23.2 g of H12MDI, 0.4 g of TiOP, 10.6 mg of U-830, 88.6 g of PP, 9.8 g of dehydrated toluene, 205.8 g of DMF, 5.3 g of IPDA, and 0.3 g of morpholine. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Comparative Example 3-2

(80) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate diol produced in Comparative Example 3-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

Comparative Example 4-2

(81) A polyurethane solution and a polyurethane film were obtained in the same manner as in Example 1-2 except that, in the polyurethane production, the polycarbonate diol produced in Comparative Example 4-1 was used and the weights of H12MDI and IPDA were changed as shown in Table 3. The results of evaluating the physical properties of the thus obtained polyurethane solution and polyurethane film are shown in Table 3.

(82) TABLE-US-00003 TABLE 3 Example Example Example Example Example Example Example 1-2 2-2 3-2 4-2 5-2 6-2 Raw materials Polycarbonate Formulation NPG/ NPG/ NPG/ NPG/ NPG/ BEPD/ for diol 14BD 14BD 14BD 14BD 14BD 14BG polyurethane (Content ratio of 3.2 0.5 1.6 5.3 7.9 4.6 production branched-chain moiety in polymer/Content ratio of carbonate group in polymer) × 100 (%) Hydroxyl value (mg- 54.0 51.2 54.1 52.6 50.7 54.8 KOH/g) Mn 2,078 2,191 2,074 2,133 2,213 2,047 Amount used (g) 98.5 90.4 90.6 90.4 90.0 79.9 H12MDI Amount used (g) 25.4 22.0 23.0 22.6 21.6 20.8 IPDA Amount used (g) 6.6 6.0 6.0 6.0 5.7 5.5 Evaluation of Molecular weight Mw 194,000 174,000 194,000 175,000 174,000 163,000 physical (in terms of polystyrene) properties of Tensile test 100% M (MPa) 5.9 5.4 5.6 6.0 6.0 6.5 polyurethane (23° C.) 300% M (MPa) 31 29 28 31 31 35 Elongation at break (%) 383 423 456 437 444 433 Breaking strerigth (MPa) 60 71 81 82 83 84 Tensile test 100% M (MPa) 16.7 16.2 17.7 18.7 19.1 20.9 (−10° C.) Solvent Oleic acid (% by 17.5 17.6 17.4 17.2 18.1 18.1 resistance test weight) Ethanol (% by weight) 18.4 18.8 19.0 20.0 21.4 18.6 Ethyl acetate (% by 89.6 98.8 88.4 98.3 112.1 98.3 weight) Storage stability of polyurethane solution ⊚ Δ ◯ ⊚ ⊚ Δ Example Comparative Comparative Comparative Comparative Example Example Example Example 1-2 2-2 3-2 4-2 Raw materials Polycarbonate Formulation 14BD NPG/ NPG/ BEPD/ for diol 14BD 16HD 14BD polyurethane (Content ratio of 0.0 23.9 3.8 33.8 production branched-chain moiety in polymer/Content ratio of carbonate group in polymer) × 100 (%) Hydroxyl value (mg- 55.7 53.9 51.5 61.2 KOH/g) Mn 2,014 2,082 2,179 1,833 Amount used (g) 90.3 90.4 80.2 80.1 H12MDI Amount used (g) 23.8 23.2 19.6 23.2 IPDA Amount used (g) 6.3 5.3 5.1 6.3 Evaluation of Molecular weight Mw 168,000 194,000 160,000 158,000 physical (in terms of polystyrene) properties of Tensile test 100% M (MPa) 6.4 8.8 — — polyurethane (23° C.) 300% M (MPa) 40 43 — — Elongation at break (%) 370 325 — — Breaking strerigth (MPa) 65 48 — — Tensile test 100% M (MPa) 18.7 38.4 — — (−10° C.) Solvent Oleic acid (% by 18.8 32.6 58.9 45.5 resistance test weight) Ethanol (% by weight) 17.5 30.6 24.1 24.3 Ethyl acetate (% by 99.7 169.4 108.0 142.6 weight) Storage stability of polyurethane solution X ⊚ — —

(83) According to Table 3, it is seen that the polyurethanes obtained from the polycarbonate diol according to one aspect of the present invention not only exhibited high flexibility at both room temperature and a low temperature and high durability against various solvents, but also yielded polyurethane solutions having a high storage stability.