ANHYDROUS ALCOHOL-ALKYLENE GLYCOL COMPOSITION, ANHYDROUS ALCOHOL-BASED URETHANE-MODIFIED POLYOL COMPOSITION, AND USES OF SAME FOR EXPOXY RESIN COMPOSITION

Abstract

The present invention relates to an anhydrosugar alcohol-alkylene glycol composition, an anhydrosugar alcohol-based urethane-modified polyol composition, and use thereof for epoxy resin composition.

Claims

1. An anhydrosugar alcohol-alkylene glycol composition comprising: (i) monoanhydrosugar alcohol-alkylene glycol; (ii) dianhydrosugar alcohol-alkylene glycol; and (iii) alkylene oxide adduct of polymer of one or more of monoanhydrosugar alcohol and dianhydrosugar alcohol, wherein (1) the number average molecular weight (Mn) of the composition is 280 to 1,000 g/mol; (2) the poly dispersity index (PDI) of the composition is 1.77 to 5.0; and (3) the hydroxyl value of the composition is 200 to 727 mgKOH/g.

2. The anhydrosugar alcohol-alkylene glycol composition of claim 1, wherein the hydroxyl equivalent weight of the composition is 78 to 280 g/eq.

3. The anhydrosugar alcohol-alkylene glycol composition of claim 1, which is that prepared from addition reaction of alkylene oxide and an anhydrosugar alcohol composition comprising i) monoanhydrosugar alcohol, ii) dianhydrosugar alcohol, and iii) polymer of one or more of monoanhydrosugar alcohol and dianhydrosugar alcohol.

4. The anhydrosugar alcohol-alkylene glycol composition of claim 3, wherein the anhydrosugar alcohol composition has (i) the number average molecular weight (Mn) of 160 to 445; (ii) the poly dispersity index (PDI) of 1.25 to 3.15; and (iii) the hydroxyl value of 645 to 900 mgKOH/g.

5. The anhydrosugar alcohol-alkylene glycol composition of claim 3, wherein the polymer of one or more of monoanhydrosugar alcohol and dianhydrosugar alcohol is one or more selected from the group consisting of polymers represented by the following formulas 1 to 5: ##STR00002## wherein: in formulas 1 to 5, each of a to d is independently an integer of 0 to 25, provided that a+b+c+d is 2 to 100.

6. The anhydrosugar alcohol-alkylene glycol composition of claim 3, wherein the alkylene oxide is a linear alkylene oxide having 2 to 8 carbons or a branched alkylene oxide having 3 to 8 carbons.

7. The anhydrosugar alcohol-alkylene glycol composition of claim 3, wherein 32 parts by weight or more of the alkylene oxide is added to 100 parts by weight of the anhydrosugar alcohol composition.

8. A method for preparing an anhydrosugar alcohol-alkylene glycol composition, comprising a step of addition reaction of an anhydrosugar alcohol composition and alkylene oxide, wherein the anhydrosugar alcohol composition comprises i) monoanhydrosugar alcohol; ii) dianhydrosugar alcohol; and iii) polymer of one or more of monoanhydrosugar alcohol and dianhydrosugar alcohol; and wherein (1) the number average molecular weight (Mn) of the prepared anhydrosugar alcohol-alkylene glycol composition is 280 to 1,000 g/mol; (2) the poly dispersity index (PDI) of the prepared anhydrosugar alcohol-alkylene glycol composition is 1.77 to 5.0; and (3) the hydroxyl value of the prepared anhydrosugar alcohol-alkylene glycol composition is 200 to 727 mgKOH/g.

9. A curing agent for epoxy resin comprising the anhydrosugar alcohol-alkylene glycol composition of claim 1.

10. A urethane-modified polyol composition prepared by urethane crosslinking reaction of the anhydrosugar alcohol-alkylene glycol composition of claim 1 and polyisocyanate, wherein the equivalent ratio of NCO group/OH group is greater than 0.1 and less than 1.7.

11. A method for preparing a urethane-modified polyol composition, comprising a step of urethane crosslinking reaction of the anhydrosugar alcohol-alkylene glycol composition of claim 1 and polyisocyanate to prepare the urethane-modified polyol composition, wherein the anhydrosugar alcohol-alkylene glycol composition and the polyisocyanate are subjected to urethane crosslinking reaction so that the equivalent ratio of NCO group/OH group becomes greater than 0.1 and less than 1.7.

12. A toughening agent for epoxy resin comprising the urethane-modified polyol composition of claim 10.

13. An epoxy resin composition comprising: (1) (a) a curing agent for epoxy resin comprising an anhydrosugar alcohol-alkylene glycol composition comprising: (i) monoanhydrosugar alcohol-alkylene glycol; (ii) dianhydrosugar alcohol-alkylene glycol; and (iii) alkylene oxide adduct of polymer of one or more of monoanhydrosugar alcohol and dianhydrosugar alcohol, wherein (1) the number average molecular weight (Mn) of the composition is 280 to 1,000 g/mol; (2) the poly dispersity index (PDI) of the composition is 1.77 to 5.0; and (3) the hydroxyl value of the composition is 200 to 727 mgKOH/g, (b) the toughening agent for epoxy resin of claim 12, or (c) a combination or (a) and (b); and (2) an epoxy resin.

14. The epoxy resin composition of claim 13, wherein the epoxy resin is selected from the group consisting of bisphenol A-epichlorohydrin resin, diglycidyl ether resin of bisphenol A, novolac type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, bicyclic epoxy resin, glycidyl ester type epoxy resin, brominated epoxy resin, bio-derived epoxy resin, epoxidized soybean oil, or combinations thereof.

15. The epoxy resin composition of claim 13, wherein the equivalent ratio of the curing agent to the epoxy resin (equivalent amount of the curing agent/equivalent amount of the epoxy resin) is 0.95 to 1.05.

16. The epoxy resin composition of claim 13, further comprising a curing catalyst.

17. The epoxy resin composition of claim 13, further comprising an additive selected from the group consisting of antioxidant, UV absorber, filler, resin modifier, silane coupling agent, diluent, colorant, defoamer, deaeration agent, dispersant, viscosity controlling agent, gloss controlling agent, wetting agent, conductivity imparting agent, or combinations thereof.

18. A cured product obtained by curing the epoxy resin composition of claim 13.

19. A molded article comprising the cured product of claim 18.

Description

EXAMPLES

[0112] <Preparation of Anhydrosugar Alcohol Composition>

Preparation Example A1: Preparation of Anhydrosugar Alcohol Composition Comprising Monoanhydrosugar Alcohol. Dianhydrosugar Alcohol and Polymer Thereof

[0113] In a 3-necked glass reactor equipped with an agitator, 1,000 g of sorbitol powder (D-sorbitol) was added and the inside temperature of the reactor was elevated to 110° C. for melting, and then 10 g of concentrated sulfuric acid (95%) was added thereto and the reaction temperature was elevated to 135° C. Then, the dehydration reaction was conducted for 4 hours under vacuum condition of 30 torr. Thereafter, the inside temperature of the reactor was lowered to 110° C., and 20 g of 50% sodium hydroxide solution was added to the dehydration reaction product solution for neutralization, and then the neutralized solution was fed into a thin film distillator (also known as short path distillator (SPD)) for distillation. At that time, the distillation was carried out at 160° C. under vacuum condition of 1 mbar, and the distilled liquid was separated. After the separation, obtained was 304 g of anhydrosugar alcohol composition comprising 31% by weight of isosorbide (dianhydrosugar alcohol), 17% by weight of sorbitan (monoanhydrosugar alcohol) and 52% by weight of polymer thereof, wherein the number average molecular weight of the composition was 257 g/mol, the poly dispersity index of the composition was 1.78, the hydroxyl value of the composition was 783 mg KOH/g, and the average number of —OH groups per molecule in the composition was 3.6.

[0114] <Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition>

Example A1: Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition with the Addition Amount of 50 Parts by Weight of Ethylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition

[0115] In a high pressure reactor equipped with an agitator, 100 g of the anhydrosugar alcohol composition obtained in Preparation Example A1 and 0.1 g of potassium hydroxide (KOH) were added and the temperature was elevated to 120° C., and then 50 g of ethylene oxide was added thereto. The reaction was then conducted at 120° C. for 3 hours to obtain 149 g of anhydrosugar alcohol-alkylene glycol composition with the addition amount of 50 parts by weight of ethylene oxide to 100 parts by weight of anhydrosugar alcohol composition.

Example A2: Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition with the Addition Amount of 300 Parts by Weight of Ethylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition

[0116] Excepting that the addition amount of ethylene oxide was changed from 50 g to 300 g, the same method as Example A1 was conducted to obtain 379 g of anhydrosugar alcohol-alkylene glycol composition with the addition amount of 300 parts by weight of ethylene oxide to 100 parts by weight of anhydrosugar alcohol composition.

Example A3: Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition with the Addition Amount of 200 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition

[0117] Excepting that 200 g of propylene oxide was used instead of ethylene oxide, the same method as Example A1 was conducted to obtain 288 g of anhydrosugar alcohol-alkylene glycol composition with the addition amount of 200 parts by weight of propylene oxide to 100 parts by weight of anhydrosugar alcohol composition.

Example A4: Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition with the Addition Amount of 400 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition

[0118] Excepting that 400 g of propylene oxide was used instead of ethylene oxide, the same method as Example A1 was conducted to obtain 471 g of anhydrosugar alcohol-alkylene glycol composition with the addition amount of 400 parts by weight of propylene oxide to 100 parts by weight of anhydrosugar alcohol composition.

Comparative Example A1: Preparation of Anhydrosugar Alcohol-Alkylene Glycol Composition with the Addition Amount of 30 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition

[0119] Excepting that 30 g of propylene oxide was used instead of ethylene oxide, the same method as Example A1 was conducted to obtain 130 g of anhydrosugar alcohol-alkylene glycol composition with the addition amount of 30 parts by weight of propylene oxide to 100 parts by weight of anhydrosugar alcohol composition.

[0120] The reactants and properties of the anhydrosugar alcohol-alkylene glycol compositions obtained in Examples A1 to A4 and Comparative Example A1 were measured by the methods explained below, and the results are shown in the following Table 1.

[0121] <Methods for Measuring Properties>

[0122] (1) Number Average Molecular Weight (Mn) and Poly Dispersity Index (PDI)

[0123] Each of the anhydrosugar alcohol-alkylene glycol compositions prepared in Examples A1 to A4 and Comparative Example A1 in an amount of 1 to 3 parts by weight was dissolved in 100 parts by weight of tetrahydrofuran, and the number average molecular weight (Mn) and poly dispersity index (PDI) were measured by using Gel Permeation Chromatography (GPC) (Agilent). The used column was PLgel 3 μm MIXED-E 300×7.5 mm (Agilent), the column temperature was 50° C., the used eluent was tetrahydrofuran with a flow rate of 0.5 mL/min, and the used standard was polymethyl methacrylate (Agilent).

[0124] (2) Hydroxyl Value

[0125] According to the hydroxyl value test standard ASTM D-4274D, the hydroxyl values of the anhydrosugar alcohol-alkylene glycol compositions were measured by conducting esterification reaction of each of the anhydrosugar alcohol-alkylene glycol compositions prepared in Examples A1 to A4 and Comparative Example A1 with excessive phthalic anhydride in the presence of imidazole catalyst and then titrating the residual phthalic anhydride with 0.5 N sodium hydroxide (NaOH).

[0126] (3) Hydroxyl Equivalent Weight

[0127] The hydroxyl equivalent weight of each of the anhydrosugar alcohol-alkylene glycol compositions prepared in Examples A1 to A4 and Comparative Example A1 was calculated according to the following equation:

Hydroxyl equivalent weight (g/eq)=56,100/Hydroxyl value

TABLE-US-00001 TABLE 1 Example Comparative Example A1 A2 A3 A4 A1 Reactants Anhydrosugar alcohol Preparation Example A1(100) Preparation Example A1(100) composition (parts by weight) Alkylene oxide EO(50) EO(300) PO(200) PO(400) PO(30) (parts by weight) Properties Number average 317 912 689 987 279 molecular weight (g/mol) Poly dispersity index 1.89 2.35 2.15 2.58 1.76 Hydroxyl value 615 237 401 221 728 (mgKOH/g) Hydroxyl equivalent 91.2 237 140 254 77.1 weight (g/eq)

[0128] <Preparation of Epoxy Resin Composition and Cured Product Thereof>

Example B1: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A1 as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0129] 32.8 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 (hydroxyl equivalent weight (HEW): 91.2 g/eq, 1 equivalent amount) and 67.2 g of diglycidyl ether of bisphenol A (DGEBA)-based bifunctional epoxy resin (YD-128, Kukdo Chemical, epoxy equivalent weight (EEW): 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition.

[0130] For a sample of cured epoxy product obtained from the above-prepared epoxy resin composition, elongation ratio was measured and the result is shown in the following Table 2.

[0131] In addition, for the above-prepared epoxy resin composition, differential scanning calorie analysis was conducted by using a differential scanning calorimeter (Q20, TA instruments). Concretely, the above-prepared epoxy resin composition was sealed within an aluminum pan and the temperature was elevated from room temperature to 250° C. with a temperature elevation rate of 10° C./minute under highly pure nitrogen atmosphere. Thereafter, the differential scanning calorie analysis was conducted until the exothermic peak disappeared. At that time, whether the epoxy resin composition was cured or not was confirmed by the measured enthalpy. The measured enthalpy is shown in the following Table 2.

Example B2: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A2 as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0132] 55.9 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A2 (HEW: 237 g/eq, 1 equivalent amount) and 44.1 g of diglycidyl ether of bisphenol A-based bifunctional epoxy resin (YD-128, Kukdo Chemical, EEW: 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Example B3: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A3 as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0133] 42.8 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 (HEW: 140 g/eq, 1 equivalent amount) and 57.2 g of diglycidyl ether of bisphenol A-based bifunctional epoxy resin (YD-128, Kukdo Chemical, EEW: 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Example B4: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A3 as the Curing Agent and Cycloaliphatic Bifunctional Epoxy Resin as the Epoxy Resin

[0134] 49.3 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 (HEW: 140 g/eq, 1 equivalent amount) and 50.7 g of cycloaliphatic bifunctional epoxy resin (Celloxide 2021p, Daicel, EEW: 137 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of 2-ethyl-4-methylimidazole (2E4M, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Example B5: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A3 as the Curing Agent and O-Cresol Novolac Epoxy Resin as the Epoxy Resin

[0135] 40.5 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 (HEW: 140 g/eq, 1 equivalent amount) and 59.5 g of O-cresol novolac epoxy resin (YDCN-500-90P, Kukdo Chemical, EEW: 206 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of triphenyl phosphine (TPP, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Example B6: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Example A4 as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0136] 57.6 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A4 (HEW: 254 g/eq, 1 equivalent amount) and 42.4 g of diglycidyl ether of bisphenol A-based bifunctional epoxy resin (YD-128, Kukdo Chemical, EEW: 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Comparative Example B1: Use of Anhydrosugar Alcohol-Alkylene Glycol Composition of Comparative Example A1 as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0137] 29.2 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Comparative Example A1 (HEW: 77.1 g/eq, 1 equivalent amount) and 70.8 g of diglycidyl ether of bisphenol A-based bifunctional epoxy resin (YD-128, Kukdo Chemical, EEW: 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

Comparative Example B2: Use of Phenol-Based Curing Agent as the Curing Agent and DGEBA-Based Epoxy Resin as the Epoxy Resin

[0138] 47.5 g of phenol-based curing agent (XLC-4L, Mitsui Chemicals, HEW: 169 g/eq, 1 equivalent amount) and 52.5 g of diglycidyl ether of bisphenol A-based bifunctional epoxy resin (YD-128, Kukdo Chemical, EEW: 187 g/eq, 1 equivalent amount) were mixed, and to 100 parts by weight of the mixture, 0.1 part by weight of N,N-dimethylbutylamine (DMBA, Sigma Aldrich) as catalyst was added to prepare an epoxy resin composition. For the above-prepared epoxy resin composition, the elongation ratio of the cured product was measured and the differential scanning calorie analysis was conducted in the same manner as Example B1, and the results are shown in the following Table 2.

[0139] <Methods for Measuring Properties>

[0140] (1) Elongation Ratio

[0141] A mold with 200 mm×200 mm size was prepared on a glass plate by using silicone rubber, and each of the epoxy resin compositions of Examples B1 to B6 and Comparative Examples B1 to B2 was put therein and kept at room temperature for stabilization. Thereafter, curing was conducted firstly at 100° C. for 2 hours, secondly at 140° C. for 1 hour, and thirdly at 200° C. for 3 hours, and the resulting product was cooled to room temperature, and taken out of the mold to prepare a sample of cured epoxy product in plate shape. For the prepared sample of cured epoxy product, the elongation ratio was measured with a rate of 10 mm/min according to ASTM D2370 standard by using a universal testing machine (INSTRON 5967).

[0142] (2) Exothermic Amount (ΔH)

[0143] By using a differential scanning calorimeter, after fixing the temperature to 150° C., the exothermic amount was measured from the time when the exothermic peak began to appear to the time when the exothermic peak disappeared.

TABLE-US-00002 TABLE 2 Exothermic Elongation Epoxy resin Curing agent Curing catalyst amount (ΔH) ratio (%) Example B1 YD-128 Example A1 DMBA 351.4 9.7 B2 YD-128 Example A2 307.8 14.1 B3 YD-128 Example A3 293.6 10.8 B4 Celloxide Example A3 2E4MI 297.5 14.5 2021p B5 YDCN-500- Example A3 TPP 314.1 8.7 90p B6 YD-128 Example A4 DMBA 298.4 13.9 Comparative B1 YD-128 Comparative DMBA 373.1 3.8 Example Example A1 B2 XLC-4L 332.1 2.2

[0144] As shown in the above Table 2, the samples of Examples B1 to B6 using an anhydrosugar alcohol-alkylene glycol composition according to the present invention as a curing agent showed good elongation ratio of 8% or higher, and good exothermic amount of 290 or higher resulting in good curing degree.

[0145] However, the sample of Comparative Example B1 prepared by using an anhydrosugar alcohol-alkylene glycol composition, wherein the addition amount of alkylene oxide was less than the specific range of the present invention and the number average molecular weight, poly dispersity index, hydroxyl value and hydroxyl equivalent weight were out of the specific ranges of the present invention, as a curing agent showed high exothermic amount resulting in good curing degree, but very poor elongation ratio of 4% or lower. Also, the sample of Comparative Example B2 prepared by using a commercially available phenol-based curing agent for general purpose showed high exothermic amount resulting in good curing degree, but very poor elongation ratio of 4% or lower.

[0146] <Urethane-Modified Polyol Composition Prepared by Urethane Crosslinking with Diisocyanate>

Example C1: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 50 Arts by Weight of Ethylene Oxide to 100 Arts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with MDI to Make the Equivalent Ratio of NCO/OH Become 1.0

[0147] In a 3-necked glass reactor equipped with an agitator, 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and 68.7 g of 4,4′-methylenediphenyl diisocyanate (MDI) (Lupranat® MI, BASF) were added, and the inside temperature of the reactor was elevated to 60° C., and then the crosslinking reaction was conducted for 1 hour with agitation. After completing the reaction, the reaction product was cooled to room temperature to obtain 118 g of polyol composition urethane-crosslinked with MDI to make the equivalent ratio of NCO/OH become 1.0.

Example C2: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 300 Parts by Weight of Ethylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with MDI to Make the Equivalent Ratio of NCO/OH Become 0.2

[0148] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A2 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and the amount of MDI was changes from 68.7 g to 5.3 g, the same method as Example C1 was conducted to obtain 55 g of polyol composition urethane-crosslinked with MDI to make the equivalent ratio of NCO/OH become 0.2.

Example C3: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 200 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with HDI to Make the Equivalent Ratio of NCO/OH Become 1.5

[0149] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and 45.1 g of hexamethylene diisocyanate (HDI, Aldrich) was used instead of MDI, the same method as Example C1 was conducted to obtain 94 g of polyol composition urethane-crosslinked with HDI to make the equivalent ratio of NCO/OH become 1.5.

Example C4: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 200 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with IPDI to Make the Equivalent Ratio of NCO/OH Become 1.0

[0150] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and 39.7 g of isophorone diisocyanate (IPDI, Aldrich) was used instead of MDI, the same method as Example C1 was conducted to obtain 89 g of polyol composition urethane-crosslinked with IPDI to make the equivalent ratio of NCO/OH become 1.0.

Example C5: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 400 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with IPDI to Make the Equivalent Ratio of NCO/OH Become 1.0

[0151] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A4 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and 21.9 g of isophorone diisocyanate (IPDI, Aldrich) was used instead of MDI, the same method as Example C1 was conducted to obtain 71 g of polyol composition urethane-crosslinked with IPDI to make the equivalent ratio of NCO/OH become 1.0.

Comparative Example C1: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 200 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with MDI to Make the Equivalent Ratio of NCO/OH Become 0.1

[0152] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and the amount of MDI was changes from 68.7 g to 4.5 g, the same method as Example C1 was conducted to obtain 54 g of polyol composition urethane-crosslinked with MDI to make the equivalent ratio of NCO/OH become 0.1.

Comparative Example C2: Preparation of Urethane-Modified Polyol Composition by Using the Addition Amount of 200 Parts by Weight of Propylene Oxide to 100 Parts by Weight of Anhydrosugar Alcohol Composition and Urethane Crosslinking with MDI to Make the Equivalent Ratio of NCO/OH Become 1.7

[0153] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A3 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and the amount of MDI was changes from 68.7 g to 76.2 g, the same method as Example C1 was conducted to obtain 126 g of polyol composition urethane-crosslinked with MDI to make the equivalent ratio of NCO/OH become 1.7.

Comparative Example C3: Failure to Prepare Urethane-Crosslinked Polyol Composition

[0154] Excepting that 50 g of the anhydrosugar alcohol-alkylene glycol composition obtained in Comparative Example A1 was used instead of the anhydrosugar alcohol-alkylene glycol composition obtained in Example A1 and the amount of MDI was changes from 68.7 g to 81.3 g, the same method as Example C1 was conducted. However, due to the poor compatibility between the anhydrosugar alcohol-alkylene glycol composition and MDI, the mixing was not facilitated, and accordingly it was not possible to prepare urethane-crosslinked polyol composition.

[0155] The reactants and properties of the urethane-modified polyol compositions obtained in Examples C1 to C5 and Comparative Examples C1 to C3 are shown in the following Table 3.

TABLE-US-00003 TABLE 3 Example Comparative Example C1 C2 C3 C4 C5 C1 C2 C3 Reactants Anhydrosugar Exam. Exam. Exam. Exam. Exam. Exam. Exam. Comp. alcohol A1 A2 A3 A3 A4 A3 A3 Exam. composition A1 Polyisocyanate MDI MDI HDI IPDI IPDI MDI MDI MDI Properties Equivalent ratio 1.0 0.2 1.5 1.0 1.0 0.1 1.7 1.0 of NCO/OH

[0156] <Preparation of Epoxy Resin Composition and Cured Product Thereof>

Examples D1 to D5 and Comparative Examples D1 to D3: Preparation of Epoxy Resin Composition and Cured Product Thereof

[0157] Diglycidyl ether of bisphenol A (DGEBA)-based epoxy resin (YD-128, Kukdo Chemical) was used as an epoxy resin, a curing agent for epoxy resin (dicyandiamide (DICY), Aldrich) and a curing promotor for epoxy resin (urea derivative (Diuron), Aldrich) stable at room temperature were used to derive curing reaction at high temperature, calcium carbonate having particle size of 21 to 33 μm (CaCO.sub.3, OMYACARB 30-CN, OMYA) was used as a filler, and each of the urethane-modified polyol compositions obtained in Examples C1 to C5 and Comparative Examples C1 to C2 was used as a toughening agent for epoxy resin.

[0158] The epoxy resin, curing agent, curing promotor, filler and toughening agent were mixed with the compositional ratio shown in the following Table 4 to prepare epoxy resin compositions of Examples D1 to D5 and Comparative Examples D1 to D3.

[0159] Concretely, in a 300 mL reaction bath having separated upper and lower parts, under vacuum, the liquid type raw materials (epoxy resin and toughening agent) were added and subjected to the first agitation at 90° C. for 20 minutes. Then, the solid type raw materials (curing agent, curing promotor and filler) were added thereto according to the determined compositional ratio, and subjected to the second agitation under the same condition for 30 minutes to prepare an epoxy resin composition.

[0160] A casting mold preheated to 120° C. was fully filled with the above-obtained epoxy resin composition and moved into a curing oven heated to 170° C., and the curing reaction was conducted for 30 minutes. For the cured product, the following property was measured and the results are shown in the following Table 4.

[0161] <Methods for Measuring Properties>

[0162] Impact Strength

[0163] According to ASTM D 256, for a sample of cured product obtained by curing each of the epoxy resin compositions obtained in Examples D1 to D5 and Comparative Examples D1 to D3, impact strength was measured. Concretely, a sample of cured product obtained in each of Examples D1 to D5 and Comparative Examples D1 to D3 was processed to have a size of 63.5 mm×12.7 mm×3 mm (length×width×thickness), and by using Izod type impact test machine (CEAST 9350, INSTRON), impact was applied to the sample of cured product by directly hitting it with pendulum, and based on the value obtained through the hitting, the impact strength was measured. At that time, notch of 2.54 mm was applied.

TABLE-US-00004 TABLE 4 Example Comparative Example D1 D2 D3 D4 D5 D1 D2 D3 Composition Amount of 100 100 100 100 100 100 100 100 epoxy resin (parts by weight) Amount of 11 11 11 11 11 11 11 11 curing agent (parts by weight) Amount of 1 1 1 1 1 1 1 1 curing promotor (parts by weight) Amount of 10 10 10 10 10 10 10 10 filler (parts by weight) Amount of 27 27 27 27 27 0 27 27 toughening agent (parts by weight) Kind of Exam. Exam. Exam. Exam. Exam. — Comp. Comp. toughening C1 C2 C3 C4 C5 Exam. Exam. agent C1 C2 Property impact 18.6 16.9 20.1 22.8 21.9 10.0 11.3 Heat strength generation (MPa) at initial stage

[0164] As shown in Table 4 above, the samples of cured product of Examples D1 to D5 according to the present invention were confirmed to exhibit good impact strength property.

[0165] However, the sample of Comparative Example D1 using no toughening agent and the sample of Comparative Example D2 using a urethane-modified polyol composition urethane-crosslinked to make the equivalent ratio of NCO/OH become 0.1 or less as a toughening agent exhibited poor impact strength.

[0166] In addition, in case of the sample of Comparative Example D3 using a urethane-modified polyol composition urethane-crosslinked to make the equivalent ratio of NCO/OH become 1.7 or more as a toughening agent, when the raw materials were mixed to prepare the epoxy resin composition, a large amount of heat was generated at initial stage, and thus it was not possible to obtain a sample of cured product suitable for property measurement.