Alkylene oxide-added polyol composition, polyurethane using same, and hot melt adhesive using same

Abstract

The present invention relates to an alkylene oxide-added polyol composition, a polyurethane using the same, and a hot-melt adhesive using the same. More specifically, the present invention relates to an alkylene oxide-added polyol composition that is produced by addition reacting a specific amount of an anhydrosugar alcohol composition containing a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol; d) an anhydrosugar alcohol derived from a polysaccharide alcohol; and e) a polymer of one or more of a) to d) with an alkylene oxide, thereby improving the bio content and adhesiveness and enabling the production of polyurethane at lower cost than petroleum-based polyols and other biopolyols, a polyurethane using the same, and a hot-melt adhesive using the same.

Description

[Technical field]

[0001] The present invention relates to an alkylene oxide-added polyol composition, a polyurethane using the same, and a hot melt adhesive using the same. More specifically, the present invention relates to an alkylene oxide-added polyol composition which is produced by addition reacting an anhydrosugar alcohol composition containing a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol; d) anhydrosugar alcohol derived from a polysaccharide alcohol; and e) a polymer of one or more of the above a) to d) with an alkylene oxide in a specific content, thereby improving the bio content and adhesiveness and enabling the production of polyurethane at a lower cost than petroleum-based polyols and other biopolyols, a polyurethane using the same, and a hot melt adhesive using the same. [Background technology]

[0002] In recent years, as awareness of environmental issues has increased, interest in polyurethane hot melt materials and the need for improving their properties have been growing. In general, hot melt adhesives are applied by melting them with heat, and therefore emit very little volatile organic solvents, leading to an expansion in their use as environmentally friendly adhesives, and attempts have been made to improve physical properties such as adhesiveness by using various components or additives (e.g., Patent Documents 1, 2, and 3).

[0003] Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end group of sugars. Generally, HOCH2 (CHOH) n They have the formula CH2OH (where n is an integer between 2 and 5) and are classified into tetritols, pentitols, hexitols and heptitols (having 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0004] Anhydrous sugar alcohols are substances formed by removing one or more water molecules from the inside of hydrogenated sugar. When one water molecule is removed, it becomes a tetraol with four hydroxyl groups in the molecule, and when two water molecules are removed, it becomes a diol with two hydroxyl groups in the molecule. They can be produced using hexitol derived from starch (e.g., Patent Documents 4 and 5). Anhydrous sugar alcohols are environmentally friendly substances derived from renewable natural resources, and have long been of interest, and production methods have been researched. Among such anhydrous sugar alcohols, isosorbide produced from sorbitol currently has the widest range of industrial applications.

[0005] Anhydrous sugar alcohols are used in various fields such as medicines such as the treatment of heart and vascular diseases, adhesives for patches, oral cleansers, solvents for compositions in the cosmetic industry, and emulsifiers in the food industry. In addition, they increase the glass transition temperature of polymeric substances such as polyester, PET, polycarbonate, polyurethane, and epoxy resin, and have the effect of improving the strength of such substances. Since they are environmentally friendly materials derived from natural products, they are very useful in the plastics industry, such as bioplastics. In addition, it is also known that anhydrous sugar alcohols can be used as adhesives, environmentally friendly plasticizers, biodegradable polymers, and environmentally friendly solvents for water-soluble lacquers.

[0006] As described above, anhydrosugar alcohols have attracted great interest due to their wide range of applications, and the level of industrial practical application is increasing.

[0007] Conventional commercial hot melt adhesives lack sufficient adhesive strength, and as they are petroleum-derived adhesives, there was a need for improvement due to environmental considerations. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Korean Patent Application Publication No. 10-2013-0119850 [Patent Document 2] Korean Patent No. 10-1370442 [Patent Document 3] Korean Patent No. 10-1709909 [Patent Document 4] Korean Patent No. 10-1079518 [Patent Document 5] Korean Patent Application Publication No. 10-2012-0066904 Summary of the Invention [Problem to be solved by the invention]

[0009] The object of the present invention is to provide an alkylene oxide-added polyol composition which is produced by addition reacting a specific content of an anhydrosugar alcohol composition comprising a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol; d) polysaccharide alcohol-derived anhydrosugar alcohol; and e) one or more polymers of the above a) to d) with an alkylene oxide, thereby improving the bio content and adhesiveness and enabling the production of polyurethane from petroleum-based polyols and other biopolyols at lower cost, as well as a polyurethane using the same and a hot melt adhesive using the same. [Means for solving the problem]

[0010] In order to solve the above-mentioned technical problems, the present invention provides a polyol composition produced by addition reacting 100 parts by weight of an anhydrosugar alcohol composition with more than 50 parts by weight and less than 4,000 parts by weight of an alkylene oxide, the anhydrosugar alcohol composition comprising: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1); d) an anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of the a) to d).

[0011] [ka] (In the formula, n is an integer of 0 to 4.)

[0012] According to another aspect of the present invention, there is provided a polyurethane prepolymer prepared from the reaction of the polyol composition of the present invention with a polyisocyanate.

[0013] In another aspect, the invention provides a chain extended polyurethane prepared by reacting a polyurethane prepolymer with a chain extender.

[0014] In another aspect, the present invention provides a method for producing a chain-extended polyurethane, comprising: (1) reacting the polyol composition of the present invention with a polyisocyanate to produce a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer with a chain extender.

[0015] In another aspect, the present invention provides a hot melt adhesive comprising the chain extended polyurethane of the present invention. Effect of the Invention

[0016] According to the present invention, a polyol composition obtained by adding an alkylene oxide to an internal dehydration product of hydrogenated sugar and / or a by-product generated after the production of various sugars can be used as a polyol for producing polyurethane. This solves the cost and environmental pollution issues that arise when the by-product is treated as industrial waste (incineration, landfill, etc.), while improving the bio content and adhesiveness in the composition, and allows polyurethane to be produced at a lower cost than petroleum-based polyols and other biopolyols. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0017] The present invention will now be described in more detail. The polyol composition of the present invention is a polyol composition produced by addition reacting 100 parts by weight of an anhydrosugar alcohol composition with more than 50 parts by weight and less than 4,000 parts by weight of an alkylene oxide, and the anhydrosugar alcohol composition comprises: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1); d) an anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of the a) to d).

[0018] [ka] (In the formula, n is an integer of 0 to 4.)

[0019] Anhydrous sugar alcohols can be produced by dehydrating hydrogenated sugars derived from natural products. Hydrogenated sugars (also called "sugar alcohols") are compounds obtained by adding hydrogen to the reducing end groups of sugars, and are generally called HOCH2 (CHOH). n They have the general formula CH2OH (where n is an integer between 2 and 5) and are classified into tetritols, pentitols, hexitols and heptitols (having 4, 5, 6 and 7 carbon atoms, respectively) according to the number of carbon atoms. Among them, hexitols with 6 carbon atoms include sorbitol, mannitol, iditol, galactitol, etc., and sorbitol and mannitol are particularly useful substances.

[0020] The anhydrosugar alcohol composition of the present invention includes a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) polysaccharide alcohol represented by the following formula (1); d) anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of the above a) to d), preferably two or more, more preferably all of them, which can be obtained by hydrogenating a glucose-containing sugar composition (e.g., a sugar composition containing disaccharides or more polysaccharides including glucose, mannose, fructose, and maltose) to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition under an acid catalyst to cause a dehydration reaction, and subjecting the obtained dehydration reaction product to thin-film distillation. More specifically, a) to e) contained in the anhydrosugar alcohol composition of the present invention may be a by-product remaining after thin-film distillation of the obtained dehydration reaction product to thin-film distillation.

[0021] A monoanhydrosugar alcohol is an anhydrosugar alcohol formed by removing one water molecule from the inside of a hydrogenated sugar, and has a tetraol form having four hydroxyl groups in the molecule.

[0022] In the present invention, the type of the a) monoanhydrosugar alcohol is not particularly limited, but may be preferably a monoanhydrosugar hexitol, more specifically, 1,4-anhydrohexitol, 3,6-anhydrohexitol, 2,5-anhydrohexitol, 1,5-anhydrohexitol, 2,6-anhydrohexitol, or a mixture of two or more thereof.

[0023] Dianhydrosugar alcohols are anhydrous sugar alcohols formed by removing two water molecules from inside a hydrogenated sugar, and have a diol form with two hydroxyl groups in the molecule, and can be produced using hexitol derived from starch. Dianhydrosugar alcohols are environmentally friendly substances derived from renewable natural resources, so they have long been attracting attention, and research on their production methods has been progressing. Among such dianhydrosugar alcohols, isosorbide produced from sorbitol is currently industrially applicable.

[0024] In the present invention, the type of the dianhydrosugar alcohol b) is not particularly limited, but may be preferably a dianhydrosugar hexitol, more specifically, 1,4:3,6-dianhydrohexitol. The 1,4:3,6-dianhydrohexitol may be isosorbide, isomannide, isoidide, or a mixture of two or more thereof.

[0025] In the present invention, c) a compound represented by the following formula (1): [ka] (In the formula, n is an integer of 0 to 4.) The polysaccharide alcohol represented by the formula (I) can be produced by hydrogenating a disaccharide or higher polysaccharide containing maltose.

[0026] In the present invention, d) the anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1) is represented by the following formula (2): [ka] (In the formula, n is an integer of 0 to 4.) A compound represented by the following formula (3): [ka] (In the formula, n is an integer of 0 to 4.) The compound may be selected from the group consisting of compounds represented by the formula:

[0027] In the present invention, e) one or more polymers of a) to d) may include one or more selected from the group consisting of condensation polymers obtained by the following condensation reactions. In the following condensation reactions, the condensation positions and condensation order between monomers are not particularly limited and can be selected without limitation within the range that can be generally predicted by a person of ordinary skill in this field: Condensation reaction of monoanhydrosugar alcohols, Condensation reaction of dianhydrosugar alcohols, Condensation reaction of polysaccharide alcohol represented by the formula (1), A condensation reaction of anhydrosugar alcohol derived from a polysaccharide alcohol represented by the formula (1), - Condensation reaction of monoanhydrosugar alcohol with dianhydrosugar alcohol, - Condensation reaction of monoanhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol with polysaccharide alcohol-derived anhydrosugar alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with polysaccharide alcohol-derived anhydrosugar alcohol represented by formula (1), A condensation reaction between a polysaccharide alcohol represented by formula (1) and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol-derived anhydrosugar alcohol represented by formula (1), A condensation reaction of a monoanhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), A condensation reaction of a dianhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), or Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol represented by formula (1), and anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1).

[0028] In one embodiment, the anhydrosugar alcohol composition of the present invention may contain, for example, a) the monoanhydrosugar alcohol in an amount of 0.1 to 20% by weight, specifically 0.6 to 20% by weight, more specifically 0.7 to 15% by weight, b) the dianhydrosugar alcohol in an amount of 0.1 to 28% by weight, specifically 1 to 25% by weight, more specifically 3 to 20% by weight, c) the polysaccharide alcohol represented by formula (1) and d) the polysaccharide alcohol-derived anhydrosugar alcohol represented by formula (1) in a total amount of 0.1 to 6.5% by weight, specifically 0.5 to 6.4% by weight, more specifically 1 to 6.3% by weight, and e) one or more polymers of a) to d) may be contained in an amount of 55 to 90% by weight, specifically 60 to 89.9% by weight, more specifically 70 to 89.9% by weight, relative to the total weight of the composition, but these are not particularly limited.

[0029] In the present invention, the content of alkylene oxide added to the anhydrous sugar alcohol composition may be more than 50 parts by weight, 55 parts by weight or more, 60 parts by weight or more, 70 parts by weight or more, 80 parts by weight or more, 90 parts by weight or more, or 100 parts by weight or more, per 100 parts by weight of the anhydrous sugar alcohol composition, and may be less than 4,000 parts by weight, 3,900 parts by weight or less, 3,700 parts by weight or less, 3,500 parts by weight or less, 3,200 parts by weight or less, or 3,000 parts by weight or less.

[0030] In one embodiment, the content of the alkylene oxide added to the anhydrosugar alcohol composition may be more than 50 parts by weight to less than 4,000 parts by weight, 60 to 3,900 parts by weight, 80 to 3,500 parts by weight, or 90 to 3,200 parts by weight, based on 100 parts by weight of the anhydrosugar alcohol composition. If the amount of alkylene oxide added is 50 parts by weight or less, the soft part (wherein the alkylene oxide acts to impart softness) that imparts flexibility in the hot melt test piece produced using the polyol composition of the present invention is reduced, and cohesive peeling that breaks the hot melt adhesive itself may occur. If the amount of alkylene oxide added is 4,000 parts by weight or more, the urethane group (wherein the urethane produced by combining the polyol and isocyanate acts to impart adhesive strength) that imparts adhesive strength in the hot melt test piece may be too small, resulting in surface peeling (such as peeling of the adhesive interface).

[0031] In one embodiment, the alkylene oxide may be a linear alkylene oxide having 2 to 8 carbon atoms or a branched alkylene oxide having 3 to 8 carbon atoms, more specifically, ethylene oxide, propylene oxide, or a combination thereof.

[0032] In the polyol composition of the present invention, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 or more, 195 or more, 200 or more, 202 or more, 205 or more, or 208 or more. The number average molecular weight (Mn) of the anhydrous sugar alcohol composition of the present invention may be 1,589 or less, 1,560 or less, 1,550 or less, 1,520 or less, 1,500 or less, 1,490 or less, or 1,480 or less.

[0033] In one embodiment, the number average molecular weight (Mn) of the anhydrous sugar alcohol composition may be 193 to 1,589, specifically 195 to 1,550, more specifically 200 to 1,520, even more specifically 202 to 1,500, and even more specifically 205 to 1,490. If the number average molecular weight of the anhydrous sugar alcohol composition is less than 193, polyurethane polymerization may be difficult when a polyol composition produced using the anhydrous sugar alcohol composition is applied to polyurethane production, and if the number average molecular weight of the anhydrous sugar alcohol composition exceeds 1,589, the adhesive strength of a hot melt adhesive using a polyurethane produced using the anhydrous sugar alcohol composition may decrease when a polyol composition produced using the anhydrous sugar alcohol composition is applied to polyurethane production.

[0034] In the polyol composition of the present invention, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 or more, 1.15 or more, 1.20 or more, 1.23 or more, or 1.25 or more. The polydispersity index (PDI) of the anhydrous sugar alcohol composition of the present invention may be 3.41 or less, 3.40 or less, 3.35 or less, 3.30 or less, 3.25 or less, 3.22 or less, or 3.19 or less.

[0035] In one embodiment, the polydispersity index (PDI) of the anhydrous sugar alcohol composition may be 1.13 to 3.41, specifically 1.13 to 3.40, more specifically 1.15 to 3.35, even more specifically 1.20 to 3.25, and even more specifically 1.23 to 3.22. If the polydispersity index of the anhydrous sugar alcohol composition is less than 1.13 or exceeds 3.41, when a polyol composition produced using the composition is applied to polyurethane production, the adhesive strength of a hot melt adhesive using the polyurethane produced may decrease.

[0036] In the polyol composition of the present invention, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.54 or more, 2.60 or more, 2.65 or more, 2.70 or more, 2.75 or more, or 2.78 or more. The average number of -OH groups per molecule in the anhydrosugar alcohol composition of the present invention may be 21.36 or less, 21.30 or less, 21.0 or less, 20.5 or less, 20.0 or less, 19.95 or less, or 19.92 or less.

[0037] More specifically, the average number of -OH groups per molecule in the anhydrosugar alcohol composition may be 2.54 to 21.36, more specifically 2.60 to 21.30, and even more specifically 2.65 to 21.0. If the average number of -OH groups per molecule in the anhydrosugar alcohol composition is less than 2.54 or exceeds 21.36, when a polyol composition produced using the composition is applied to polyurethane production, the adhesive strength of a hot melt adhesive using the produced polyurethane may decrease.

[0038] In one embodiment, the anhydrous sugar alcohol composition of the present invention may be produced by hydrogenating a glucose-containing sugar composition (e.g., a sugar composition containing disaccharides or higher polysaccharides including glucose, mannose, fructose, and maltose) to produce a hydrogenated sugar composition, heating the obtained hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and thin-film distilling the obtained dehydration reaction product. Specifically, the anhydrous sugar alcohol composition of the present invention may be a by-product remaining after thin-film distillation of the obtained dehydration reaction product to obtain a thin-film distillation liquid.

[0039] More specifically, a glucose-containing saccharide composition is hydrogenated under hydrogen pressure conditions of 30 atm to 80 atm and heating conditions of 110°C to 135°C to produce a hydrogenated sugar composition, the resulting hydrogenated sugar composition is dehydrated under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105°C to 200°C to obtain a dehydration reaction product, and the resulting dehydration reaction product is thin-film distilled under reduced pressure conditions of 2 mbar or less and heating conditions of 150°C to 175°C, but the reaction conditions are not limited to these.

[0040] The glucose content of the glucose-containing saccharide composition may be 41% by weight or more, 42% by weight or more, 45% by weight or more, 47% by weight or more, or 50% by weight or more, or 99.5% by weight or less, 99% by weight or less, 98.5% by weight or less, 98% by weight or less, 97.5% by weight or less, or 97% by weight or less, for example, 41 to 99.5% by weight, 45 to 98.5% by weight, or 50 to 98% by weight. If the glucose content in the saccharide composition is less than 41% by weight, the number average molecular weight, the average number of -OH groups per molecule, and the polydispersity index of the anhydrous sugar alcohol composition may be too high, and the adhesive strength of the polyurethane hot melt adhesive may be weakened, and if it exceeds 99.5% by weight, the number average molecular weight and polydispersity index of the polyol composition may be too low, and the adhesive strength of the polyurethane hot melt adhesive may be reduced.

[0041] The content of polysaccharide alcohol (disaccharide or higher sugar alcohol) contained in the hydrogenated sugar composition may be 0.8% by weight or more, 1% by weight or more, 2% by weight or more, or 3% by weight or more, and may be 57% by weight or less, 55% by weight or less, 52% by weight or less, 50% by weight or less, or 48% by weight or less, for example, 0.8 to 57% by weight, 1 to 55% by weight, or 3 to 50% by weight, based on the total dry weight of the hydrogenated sugar composition (here, dry weight means the weight of the solid content remaining after removing water from the hydrogenated sugar composition). If the content of polysaccharide alcohol in the hydrogenated sugar composition is less than 0.8% by weight, when a polyol composition is produced using such a hydrogenated sugar composition and a polyurethane hot melt adhesive is produced by applying such a polyol composition, the adhesive strength of the polyurethane hot melt adhesive may decrease. If the content of polysaccharide alcohol in the hydrogenated sugar composition exceeds 57% by weight, the viscosity of the polyol composition produced using such a hydrogenated sugar composition may become very high, and the processability of the polyurethane hot melt adhesive may decrease. Furthermore, the more polyol groups there are in the produced polyurethane hot melt adhesive, the more excessive the isocyanate that reacts with these groups becomes, and the stronger the curing becomes, resulting in a decrease in adhesive strength.

[0042] In another aspect, the present invention provides a method for producing a polyol composition, comprising a step of performing an addition reaction between an anhydrosugar alcohol composition and an alkylene oxide, in which more than 50 parts by weight and less than 4,000 parts by weight of alkylene oxide are added to 100 parts by weight of the anhydrosugar alcohol composition, and the anhydrosugar alcohol composition comprises: a) a monoanhydrosugar alcohol; b) a dianhydrosugar alcohol; c) a polysaccharide alcohol represented by formula (1); d) anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1); and e) one or more polymers of a) to d).

[0043] In the method for producing a polyol composition of the present invention, the anhydrous sugar alcohol composition and the alkylene oxide are as described above.

[0044] In another aspect, the invention provides a polyurethane prepolymer prepared by reacting the polyol composition of the invention with a polyisocyanate.

[0045] In another aspect, the invention provides a chain extended polyurethane prepared by reacting the polyurethane prepolymer of the invention with a chain extender.

[0046] In another aspect, the present invention provides a method for producing a chain-extended polyurethane, comprising: (1) reacting the polyol composition of the present invention with a polyisocyanate to produce a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer with a chain extender.

[0047] In the method for producing a chain-extended polyurethane of the present invention, the polyurethane prepolymer can be obtained by reacting the polyol composition with a polyisocyanate. For example, the polyol composition and polyisocyanate that have been thoroughly vacuum-dried at 50 to 100°C, preferably 70 to 90°C, for 12 to 36 hours, preferably 20 to 28 hours, are charged into a four-neck reactor, and then reacted for 0.1 to 5 hours, preferably 0.5 to 2 hours, under a nitrogen atmosphere while maintaining a temperature of 50 to 100°C, preferably 50 to 70°C, to produce the polyurethane prepolymer.

[0048] The polyisocyanate compound that can be used in the present invention is not particularly limited, but specific examples thereof include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4'-methylenediphenyl diisocyanate (MDI), 2,4-methylenediphenyl diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3 Aromatic polyisocyanate compounds such as '-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4',4"-triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11 - Aliphatic polyisocyanate compounds such as undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethyl caproate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) carbonate, and 2-isocyanatoethyl-2,6-diisocyanatohexanoate; or isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane diisocyanate and alicyclic polyisocyanate compounds such as methylcyclohexylene diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis(2-isocyanatoethyl)-4-cyclohexene-1,2-diethyl azodicarboxylate, 2,5-norbornane diisocyanate, and 2,6-norbornane diisocyanate. These polyisocyanate compounds can be used alone or in combination of two or more.

[0049] The chain extender used in the method for producing the chain-extended polyurethane of the present invention is not particularly limited, and any conventional chain extender used in the production of polyurethane can be used without limitation. For example, the chain extender can be selected from the group consisting of 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylenediamine, dimethylhydrazine, 1,6-hexamethylenebishydrazine, hexamethylenediamine, isophoronediamine, diaminophenylmethane, or a combination thereof, but is not limited thereto.

[0050] In the method for producing a chain-extended polyurethane of the present invention, a chain extender is added to the polyurethane prepolymer, the mixture is then poured into a coated mold, and cured at 80°C to 200°C, preferably 100°C to 150°C, for 10 hours to 30 hours, preferably 15 hours to 25 hours, to produce a chain-extended polyurethane.

[0051] In another aspect, the present invention provides a hot melt adhesive comprising the chain extended polyurethane of the present invention, which melts appropriately at the correct temperature (e.g., 180° C.) and can be used in hot melt adhesive applications.

[0052] The hot melt adhesive of the present invention may further comprise additives commonly used in hot melt adhesives.

[0053] The present invention will be described in more detail with reference to the following examples and comparative examples, which, however, are not intended to limit the scope of the present invention. EXAMPLES

[0054] <Production of anhydrosugar alcohol composition> Preparation Example 1: Preparation of polyol composition using 97% glucose by weight and thin film distillation apparatus A glucose product having a purity of 97% was hydrogenated in the presence of a nickel catalyst at 125°C under a hydrogen pressure of 60 atm to obtain 1,819 g of a liquid hydrogenated sugar composition having a concentration of 55% by weight (solid content: 96% by weight of sorbitol, 0.9% by weight of mannitol, and 3.1% by weight of polysaccharide alcohols of disaccharides or higher). This composition was placed in a stirred batch reactor and concentrated by heating to 100°C to obtain 1,000 g of a concentrated hydrogenated sugar composition. 1,000 g of the concentrated hydrogenated sugar composition and 9.6 g of sulfuric acid were added to the reactor. Then, the internal temperature of the reactor was raised to about 135°C, and a dehydration reaction was carried out under reduced pressure conditions of about 45 mmHg to convert to anhydrous sugar alcohol. After the completion of the dehydration reaction, the temperature of the reaction product was cooled to below 110°C, and about 15.7 g of 50% aqueous sodium hydroxide solution was added to neutralize the reaction product. Then, the temperature was cooled to below 100°C, and the reaction product was concentrated under reduced pressure conditions of 45 mmHg for more than 1 hour to remove residual moisture and low boiling point substances, and about 831 g of a converted anhydrous sugar alcohol solution was obtained. The converted anhydrous sugar alcohol solution obtained was analyzed by gas chromatography, and the amount of conversion to isosorbide was 71.9 wt%, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.6% using this. 831 g of the converted anhydrous sugar alcohol solution obtained above was placed in a thin film distillation apparatus (SPD) and distilled. At this time, distillation was performed at a temperature of 160° C. and a vacuum pressure of 1 mbar, and about 589 g of distillate was obtained (distillation yield: about 70.9%). At this time, the purity of isosorbide in the distillate was measured and found to be 96.8%, and the distillation yield of isosorbide calculated from this was 95.3%. After separation of the distillate, about 242 g of an anhydrosugar alcohol composition was obtained, which contained 11.5 wt% isosorbide (dianhydrosugar alcohol), 0.4 wt% isomannide (dianhydrosugar alcohol), 7.4 wt% sorbitan (monoanhydrosugar alcohol), 2.5 wt% disaccharide or higher polysaccharide alcohols and anhydrosugar alcohols derived therefrom, and 78.2 wt% polymers thereof, and had a number average molecular weight of 208 g / mol, a polydispersity index of 1.25, a hydroxyl value of 751 mgKOH / g, and an average number of -OH groups per molecule in the composition of 2.78.

[0055] Preparation Example 2: Preparation of a polyol composition using a sugar composition containing 85.2% by weight of glucose and a thin film distillation apparatus A hydrogenation reaction was carried out in the same manner as in Production Example 1, except that a 85.2% glucose-containing saccharide composition (85.2% glucose and 14.8% mannose, fructose and polysaccharides (disaccharides or higher such as maltose) in total) was used instead of the 97% pure glucose product, to obtain 1,852 g of a liquid hydrogenated sugar composition with a concentration of 54% by weight (solid content basis, 84.1% sorbitol, 2.8% mannitol and 13.1% polysaccharide alcohols of disaccharides or higher). This composition was placed in a stirred batch reactor and heated to 100°C for concentration, to obtain 1,000 g of concentrated hydrogenated sugar composition. Except for changing the content of sulfuric acid from 9.6 g to 8.4 g and the content of 50% sodium hydroxide aqueous solution from 15.7 g to 13.7 g, 1,000 g of the concentrated hydrogenated sugar composition was dehydrated and converted into anhydrous sugar alcohol in the same manner as in Production Example 1. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained weighed about 846 g, and the converted anhydrous sugar alcohol solution was analyzed by gas chromatography, and the amount of conversion to isosorbide was 61.7 wt %, and the molar conversion rate of sorbitol to isosorbide was calculated to be 77.4%. The obtained converted anhydrosugar alcohol solution (846 g) was thin-film distilled in the same manner as in Preparation Example 1 to obtain about 528 g of a distillate (distillation yield: about 62.4%). The purity of isosorbide in the distillate was measured to be 96.5%, and the distillation yield of isosorbide calculated from this was 97.6%. After separating the distillate, about 318 g of anhydrosugar alcohol composition was obtained, which contained 4.0 wt% isosorbide (dianhydrosugar alcohol), 1.6 wt% isomannide (dianhydrosugar alcohol), 2.1 wt% sorbitan (monohydrosugar alcohol), 5.1 wt% disaccharide or higher polysaccharide alcohols and anhydrosugar alcohols derived therefrom, and 87.2 wt% of their polymers, and had a number average molecular weight of 720 g / mol, a polydispersity index of 2.54, a hydroxyl value of 754 mgKOH / g, and an average number of -OH groups per molecule in the composition of 9.68.

[0056] Preparation Example 3: Preparation of a polyol composition using a sugar composition containing 50.2% by weight of glucose and a thin film distillation apparatus A hydrogenation reaction was carried out in the same manner as in Production Example 1, except that a 50.2 wt% glucose-containing saccharide composition (50.2 wt% glucose and 49.8 wt% total of mannose, fructose and polysaccharides (disaccharides or higher sugars such as maltose)) was used instead of the 97% pure glucose product, to obtain 1,819 g of a liquid hydrogenated sugar composition with a concentration of 55 wt% (solid content basis, 48.5 wt% sorbitol, 3.6 wt% mannitol, 47.9 wt% polysaccharide alcohols of disaccharides or higher). This composition was placed in a stirred batch reactor and heated to 100°C to concentrate, yielding 1,000 g of concentrated hydrogenated sugar composition. Except for changing the content of sulfuric acid from 9.6 g to 4.85 g, the content of 50% sodium hydroxide aqueous solution from 15.7 g to 7.9 g, and the reaction temperature to 120° C., 1,000 g of the concentrated hydrogenated sugar composition was dehydrated and converted into anhydrous sugar alcohol in the same manner as in Production Example 1. As a result of the dehydration reaction, the converted anhydrous sugar alcohol solution obtained was about 890 g, and the converted anhydrous sugar alcohol solution was analyzed by gas chromatography, and the conversion amount of isosorbide was 33.7 wt %. Using this, the molar conversion rate of sorbitol to isosorbide was calculated to be 77.1%. The obtained converted anhydrosugar alcohol solution (890 g) was thin-film distilled in the same manner as in Preparation Example 1 to obtain about 304 g of a distillate (distillation yield: about 34.2%). The purity of isosorbide in the distillate was measured to be 96.9%, and the distillation yield of isosorbide calculated from this was 98.3%. After separating the distillate, about 586 g of anhydrosugar alcohol composition was obtained, which contained 0.9 wt% isosorbide (dianhydrosugar alcohol), 2.1 wt% isomannide (dianhydrosugar alcohol), 0.9 wt% sorbitan (monohydrosugar alcohol), 6.2 wt% of polysaccharide alcohols of disaccharides or higher and anhydrosugar alcohols derived therefrom, and 89.9 wt% of their polymers, and had a number average molecular weight of 1,480 g / mol, a polydispersity index of 3.19, a hydroxyl value of 755 mgKOH / g, and an average number of -OH groups per molecule in the composition of 19.92.

[0057] <Production of alkylene oxide-added polyol composition> Example A1: Polyol composition in which 100 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1 100 parts by weight (100g) of the anhydrous sugar alcohol composition of Preparation Example 1 and 0.3g of KOH were placed in a pressure reactor, and pressurized with nitrogen and vented three times. The temperature in the reactor was then raised to 100°C to remove moisture, and after all moisture was removed, 100 parts by weight (100g) of ethylene oxide was slowly injected and reacted at 100°C to 140°C. Then, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the temperature in the reactor was maintained at 100°C to 120°C while stirring for 1 to 5 hours. The amount of residual metal was monitored, and when the metal was completely removed and no longer detectable, the temperature in the reactor was cooled to 60°C to 90°C, and the mixture was filtered. The filtrate was then purified with an ion exchange resin (UPRM200; manufactured by Samyang Corporation) to obtain a polyol composition.

[0058] Example A2: A polyol composition in which 1,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

[0059] Example A3: A polyol composition in which 3,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

[0060] Example A4: A polyol composition in which 100 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

[0061] Example A5: A polyol composition in which 1,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

[0062] Example A6: A polyol composition in which 3,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

[0063] Example A7: Polyol composition in which 100 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2 A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1.

[0064] Example A8: A polyol composition in which 1,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 2 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

[0065] Example A9: A polyol composition in which 3,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 2 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 3,000 parts by weight (1,000 g).

[0066] Example A10: A polyol composition in which 100 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

[0067] Example A11: A polyol composition in which 1,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

[0068] Example A12: A polyol composition in which 3,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

[0069] Example A13: A polyol composition in which 100 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1.

[0070] Example A14: A polyol composition in which 1,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 3 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 1,000 parts by weight (1,000 g).

[0071] Example A15: A polyol composition in which 3,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 3 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 3,000 parts by weight (3,000 g).

[0072] Example A16: A polyol composition in which 100 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 100 parts by weight (100 g) of propylene oxide was used instead of ethylene oxide.

[0073] Example A17: A polyol composition in which 1,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 1,000 parts by weight (1,000 g) of propylene oxide was used instead of ethylene oxide.

[0074] Example A18: A polyol composition in which 3,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 3,000 parts by weight (3,000 g) of propylene oxide was used instead of ethylene oxide.

[0075] Example A19: A polyol composition obtained by adding 50 parts by weight of ethylene oxide and then 50 parts by weight of propylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. 100 parts by weight (100g) of the anhydrous sugar alcohol composition of Preparation Example 1 and 0.3g of KOH were placed in a pressure reactor, and pressurized with nitrogen and vented three times. Then, the temperature in the reactor was raised to 100°C to remove moisture, and after the moisture was completely removed, 50 parts by weight (50g) of ethylene oxide was slowly injected and an addition reaction was carried out at 100°C to 140°C. Then, 50 parts by weight (50g) of propylene oxide was slowly injected and an addition reaction was carried out at 100°C to 140°C. Then, 4g of a metal adsorbent (Ambosol MP20) was added to remove metals and by-products, and the temperature in the reactor was maintained at 100°C to 120°C while stirring for 1 to 5 hours. The amount of residual metal was monitored, and when the metal was completely removed and no longer detected, the temperature in the reactor was cooled to 60°C to 90°C, and the mixture was filtered. The filtrate was purified with an ion exchange resin (UPRM200; manufactured by Samyang Corporation) to obtain a polyol composition.

[0076] Example A20: A polyol composition obtained by adding 500 parts by weight of ethylene oxide and then 500 parts by weight of propylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A19, except that the content of ethylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g) and the content of propylene oxide was changed from 50 parts by weight (50 g) to 500 parts by weight (500 g).

[0077] Example A21: A polyol composition obtained by adding 500 parts by weight of propylene oxide and then 500 parts by weight of ethylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A19, except that 100 parts by weight (100 g) of anhydrous sugar alcohol composition was subjected to an addition reaction with 500 parts by weight (500 g) of propylene oxide, and then 500 parts by weight (500 g) of ethylene oxide was added.

[0078] Example A22: A polyol composition obtained by adding 1,500 parts by weight of propylene oxide and then 1,500 parts by weight of ethylene oxide to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A19, except that 100 parts by weight (100 g) of anhydrous sugar alcohol composition was subjected to an addition reaction with 1,500 parts by weight (1,500 g) of propylene oxide, and then 1,500 parts by weight (1,500 g) of ethylene oxide was added.

[0079] Comparative Example A1: A polyol composition in which 50 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

[0080] Comparative Example A2: A polyol composition in which 4,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g).

[0081] Comparative Example A3: A polyol composition in which 50 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

[0082] Comparative Example A4: A polyol composition in which 4,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 1. A polyol composition was obtained in the same manner as in Example A1, except that 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

[0083] Comparative Example A5: A polyol composition in which 50 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 2 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

[0084] Comparative Example A6: A polyol composition in which 4,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 2 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g).

[0085] Comparative Example A7: A polyol composition in which 50 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

[0086] Comparative Example A8: A polyol composition in which 4,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 2. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 2 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

[0087] Comparative Example A9: A polyol composition in which 50 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 3 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 50 parts by weight (50 g).

[0088] Comparative Example A10: A polyol composition in which 4,000 parts by weight of ethylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Preparation Example 3 was used instead of the anhydrous sugar alcohol composition of Preparation Example 1, and the amount of ethylene oxide added was changed from 100 parts by weight (100 g) to 4,000 parts by weight (4,000 g).

[0089] Comparative Example A11: A polyol composition in which 50 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 50 parts by weight (50 g) of propylene oxide was used instead of ethylene oxide.

[0090] Comparative Example A12: A polyol composition in which 4,000 parts by weight of propylene oxide is added to 100 parts by weight of the anhydrous sugar alcohol composition of Production Example 3. A polyol composition was obtained in the same manner as in Example A1, except that 100 parts by weight (100 g) of the anhydrous sugar alcohol composition of Production Example 3 was used instead of the anhydrous sugar alcohol composition of Production Example 1, and 4,000 parts by weight (4,000 g) of propylene oxide was used instead of ethylene oxide.

[0091] [Method for measuring yield of anhydrosugar alcohol composition] 1) Molar conversion rate to isosorbide (ISB) ISB molar conversion rate (%) = (moles of isosorbide produced / moles of sorbitol used) x 100 (%)

[0092] 2) Isosorbide (ISB) conversion amount The content (wt%) of isosorbide in the converted anhydrous sugar alcohol solution was measured by gas chromatography analysis, and the amount of converted isosorbide indicates the purity of isosorbide (ISB) in the converted anhydrous sugar alcohol solution.

[0093] 3) Distillation yield Distillation yield (%) = [mass of distillate (g) / mass of converted anhydrous sugar alcohol solution (g)] x 100 (%)

[0094] 4) Isosorbide (ISB) distillation yield ISB distillation yield (%) = [mass of isosorbide in the distillate (%) / mass of isosorbide in the converted anhydrous sugar alcohol solution (g)] × 100 (%)

[0095] [Method for measuring physical properties of anhydrous sugar alcohol composition] 1) Number average molecular weight (Mn) and polydispersity index (PDI) 1-3 parts by weight of the anhydrous sugar alcohol composition prepared in the above Examples and Comparative Examples was dissolved in N,N-dimethylformamide, and the number average molecular weight (Mn) and polydispersity index (PDI) were measured using a gel permeation chromatography (GPC) device (Agilent). The column used was PLgel 3μm MIXED-E 300×7.5mm (Agilent), the column temperature was 50°C, the developing solvent used was N,N-dimethylformamide containing 0.05M NaBr, flowed at 0.5mL / min, and polystyrene (Aldrich) was used as the standard substance.

[0096] 2) Hydroxyl value Each of the anhydrosugar alcohol compositions produced in the above Preparation Examples was esterified with excess phthalic anhydride under imidazole catalysis in accordance with the hydroxyl value test standard ASTM D-4274D, and the hydroxyl value of the anhydrosugar alcohol composition was then measured by titrating the remaining phthalic anhydride with 0.5N sodium hydroxide (NaOH).

[0097] 3) Average number of -OH groups per molecule The average number of -OH groups per molecule in the polyol composition was calculated according to the following formula: [Average number of -OH groups per molecule] = (hydroxyl value × number average molecular weight) / 56,100

[0098] <Production of polyurethane using alkylene oxide-added polyol composition> Example B1: Preparation of chain-extended polyurethane using the polyol composition of Example A1 as polyol and isosorbide as chain extender 100.00 g of the polyol composition of Example A1, which was thoroughly vacuum-dried at 80° C. for 24 hours, and 420.35 g of 4,4'-methylenediphenyl diisocyanate (MDI) were added to a four-neck reactor, and reacted for 1 hour while maintaining a temperature of 60° C. under a nitrogen atmosphere to produce a polyurethane prepolymer. Then, when the measured NCO% of the polyurethane prepolymer reached the theoretical NCO%, 61.37 g of isosorbide was added as a chain extender and mixed. The mixture was placed in a silicone-coated mold and cured at 110° C. for 16 hours to produce a chain-extended polyurethane.

[0099] Example B2: Preparation of chain-extended polyurethane using the polyol composition of Example A2 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A2 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 95.50 g, and the content of isosorbide was changed from 61.37 g to 13.94 g.

[0100] Example B3: Preparation of chain-extended polyurethane using the polyol composition of Example A3 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A3 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.71 g, and the content of isosorbide was changed from 61.37 g to 5.07 g.

[0101] Example B4: Preparation of chain-extended polyurethane using the polyol composition of Example A4 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A4 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 395.80 g, and the content of isosorbide was changed from 61.37 g to 57.78 g.

[0102] Example B5: Preparation of chain-extended polyurethane using the polyol composition of Example A5 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A5 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 84.67 g, and the content of isosorbide was changed from 61.37 g to 12.36 g.

[0103] Example B6: Preparation of chain-extended polyurethane using the polyol composition of Example A6 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A6 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 30.82 g, and the content of isosorbide was changed from 61.37 g to 4.50 g.

[0104] Example B7: Preparation of chain extended polyurethane using the polyol composition of Example A7 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A7 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 422.84 g, and the content of isosorbide was changed from 61.37 g to 61.73 g.

[0105] Example B8: Preparation of chain extended polyurethane using the polyol composition of Example A8 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A8 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 96.07 g, and the content of isosorbide was changed from 61.37 g to 14.03 g.

[0106] Example B9: Preparation of chain extended polyurethane using the polyol composition of Example A9 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A9 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 34.91 g, and the content of isosorbide was changed from 61.37 g to 5.10 g.

[0107] Example B10: Preparation of chain-extended polyurethane using the polyol composition of Example A10 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A10 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 398.14 g, and the content of isosorbide was changed from 61.37 g to 58.13 g.

[0108] Example B11: Preparation of chain-extended polyurethane using the polyol composition of Example A11 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A11 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 85.17 g, and the content of isosorbide was changed from 61.37 g to 12.43 g.

[0109] Example B12: Preparation of chain-extended polyurethane using the polyol composition of Example A12 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A12 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.01 g, and the content of isosorbide was changed from 61.37 g to 4.50 g.

[0110] Example B13: Preparation of chain-extended polyurethane using the polyol composition of Example A13 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A13 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 423.31 g, and the content of isosorbide was changed from 61.37 g to 61.80 g.

[0111] Example B14: Preparation of chain-extended polyurethane using the polyol composition of Example A14 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A14 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 96.17 g, and the content of isosorbide was changed from 61.37 g to 14.04 g.

[0112] Example B15: Preparation of chain-extended polyurethane using the polyol composition of Example A15 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A15 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 34.95 g, and the content of isosorbide was changed from 61.37 g to 5.10 g.

[0113] Example B16: Preparation of chain-extended polyurethane using the polyol composition of Example A16 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A16 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 398.59 g, and the content of isosorbide was changed from 61.37 g to 58.19 g.

[0114] Example B17: Preparation of chain-extended polyurethane using the polyol composition of Example A17 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A17 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 85.26 g, and the content of isosorbide was changed from 61.37 g to 12.45 g.

[0115] Example B18: Preparation of chain-extended polyurethane using the polyol composition of Example A18 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A18 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 31.04 g, and the content of isosorbide was changed from 61.37 g to 4.53 g.

[0116] Example B19: Preparation of chain-extended polyurethane using the polyol composition of Example A19 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A19 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 506.81 g, and the content of isosorbide was changed from 61.37 g to 73.99 g.

[0117] Example B20: Preparation of chain-extended polyurethane using the polyol composition of Example A20 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A20 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 158.73 g, and the content of isosorbide was changed from 61.37 g to 23.17 g.

[0118] Example B21: Preparation of chain-extended polyurethane using the polyol composition of Example A21 as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A21 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 158.71 g, and the content of isosorbide was changed from 61.37 g to 23.15 g.

[0119] Example B22: Preparation of chain-extended polyurethane using the polyol composition of Example A22 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Example A22 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 62.46 g, and the content of isosorbide was changed from 61.37 g to 9.12 g.

[0120] Comparative Example B1: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A1 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A1 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 516.28 g, and the content of isosorbide was changed from 61.37 g to 75.37 g.

[0121] Comparative Example B2: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A2 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A2 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.03 g, and the content of isosorbide was changed from 61.37 g to 3.80 g.

[0122] Comparative Example B3: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A3 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A3 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 497.34 g, and the content of isosorbide was changed from 61.37 g to 72.61 g.

[0123] Comparative Example B4: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A4 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A4 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.39 g, and the content of isosorbide was changed from 61.37 g to 3.41 g.

[0124] Comparative Example B5: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A5 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A5 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 519.33 g, and the content of isosorbide was changed from 61.37 g to 75.82 g.

[0125] Comparative Example B6: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A6 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A6 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.19 g, and the content of isosorbide was changed from 61.37 g to 3.82 g.

[0126] Comparative Example B7: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A7 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A7 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 500.28 g, and the content of isosorbide was changed from 61.37 g to 73.04 g.

[0127] Comparative Example B8: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A8 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A8 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.53 g, and the content of isosorbide was changed from 61.37 g to 3.43 g.

[0128] Comparative Example B9: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A9 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A9 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 519.91 g, and the content of isosorbide was changed from 61.37 g to 75.90 g.

[0129] Comparative Example B10: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A10 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A10 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 26.21 g, and the content of isosorbide was changed from 61.37 g to 3.83 g.

[0130] Comparative Example B11: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A11 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A11 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 500.84 g, and the content of isosorbide was changed from 61.37 g to 73.12 g.

[0131] Comparative Example B12: Preparation of a chain-extended polyurethane using the polyol composition of Comparative Example A12 as the polyol and isosorbide as the chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of the polyol composition of Comparative Example A12 was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 23.55 g, and the content of isosorbide was changed from 61.37 g to 3.44 g.

[0132] Comparative Example B13: Preparation of chain-extended polyurethane using PTMEG as polyol and isosorbide as chain extender A chain-extended polyurethane was produced in the same manner as in Example B1, except that 100.00 g of commercially available polytetramethylene ether glycol (PTMEG, weight average molecular weight 1,000) was used instead of the polyol composition of Example A1, the content of 4,4'-methylenediphenyl diisocyanate (MDI) was changed from 420.35 g to 50.05 g, and the content of isosorbide was changed from 61.37 g to 14.61 g.

[0133] <Production of hot melt test pieces> Each of the chain-extended polyurethanes prepared in Examples B1 to B22 and Comparative Examples B1 to B13 was applied to two pieces of stainless steel (20 mm x 100 mm) in a uniform size (20 mm x 20 mm), and then a pressure of 1 MPa was applied for 10 minutes at a temperature of 180°C using a hot press to prepare test pieces for measuring adhesive strength. The adhesive strength of the test pieces was measured as follows, and the results are shown in Table 1 below.

[0134] [Physical property measurement method] (1) Adhesive strength The measurement was performed at a speed of 5 mm / min using a UTM (Instron 5967 manufactured by Instron Corp.) Specifically, the adhesive strength of each hot melt test piece was measured five times in total, and the average value was calculated.

[0135] [Table 1-1]

[0136] [Table 1-2]

[0137] As shown in Table 1 above, it was confirmed that the hot-melt test pieces of Examples B1 to B22 of the present invention exhibited excellent adhesive strength, and improved economic efficiency was achieved through cost reduction. However, in the case of the hot melt test pieces of Comparative Examples B1, B3, B5, B7, B9 and B11, it was confirmed that the soft parts that impart flexibility to the hot melt test pieces were too small, resulting in cohesive peeling (referring to the case where the hot melt adhesive itself breaks down).In the case of the hot melt test pieces of Comparative Examples B2, B4, B6, B8, B10 and B12, it was confirmed that the soft parts that impart adhesive strength to the hot melt test pieces were too small, resulting in surface peeling (referring to the case where the adhesive interface peels off). On the other hand, the hot melt test piece of Comparative Example B13, which used PTMEG, a conventional commercially available polyol, melted too much at a temperature of 180°C and flowed down, and the adhesion between the two stainless steel sheets was not uniform, so it was possible to measure it.

Claims

1. A polyol composition produced by addition reaction of 100 parts by weight of an anhydrous sugar alcohol composition with more than 50 parts by weight to less than 4,000 parts by weight of an alkylene oxide, The anhydrosugar alcohol composition comprises: a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1): d) anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of a) to d); 1. A polyol composition comprising: [Formula 1] (In the formula, n is an integer from 0 to 4.)

2. The polyol composition according to claim 1, wherein the anhydrosugar alcohol composition satisfies the following i) to iii): i) the number average molecular weight (Mn) of the anhydrosugar alcohol composition is 193 to 1,589 g / mol; ii) the polydispersity index (PDI) of the anhydrosugar alcohol composition is from 1.13 to 3.41; iii) the average number of --OH groups per molecule in the anhydrosugar alcohol composition is from 2.54 to 21.

36.

3. d) The polysaccharide alcohol-derived anhydrosugar alcohol represented by formula (1) is converted into an anhydrosugar alcohol represented by formula (2): [chemical 2] (In the formula, n is an integer from 0 to 4.) a compound represented by the following formula (3): [C3] (In the formula, n is an integer from 0 to 4.) 2. The polyol composition according to claim 1, wherein the compound is selected from the group consisting of compounds represented by the formula:

4. 2. The polyol composition of claim 1, wherein a) the monoanhydrosugar alcohol is a monoanhydrosugar hexitol.

5. 2. The polyol composition of claim 1, wherein the dianhydrosugar alcohol is a dianhydrosugar hexitol.

6. e) The polyol composition according to claim 1, wherein the one or more polymers of a) to d) include one or more selected from the group consisting of condensation polymers produced by the following condensation reaction: - Condensation reaction of monoanhydrosugar alcohols, - Condensation reaction of dianhydrosugar alcohols, - Condensation reaction of polysaccharide alcohol represented by formula (1), - A condensation reaction of anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol with dianhydrosugar alcohol, - Condensation reaction of monoanhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - A condensation reaction of a monoanhydrosugar alcohol with an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - Condensation reaction of dianhydrosugar alcohol with polysaccharide alcohol represented by formula (1), - A condensation reaction of a dianhydrosugar alcohol with an anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - A condensation reaction between a polysaccharide alcohol represented by formula (1) and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and polysaccharide alcohol represented by formula (1), - Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol and anhydrosugar alcohol derived from a polysaccharide alcohol represented by formula (1), - a condensation reaction of a monoanhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), - A condensation reaction of a dianhydrosugar alcohol, a polysaccharide alcohol represented by formula (1), and an anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1), or Condensation reaction of monoanhydrosugar alcohol, dianhydrosugar alcohol, polysaccharide alcohol represented by formula (1), and anhydrosugar alcohol derived from the polysaccharide alcohol represented by formula (1).

7. A method for producing a polyol composition, comprising a step of subjecting an anhydrosugar alcohol composition to an addition reaction with an alkylene oxide, Addition reacting more than 50 parts by weight and less than 4,000 parts by weight of an alkylene oxide with 100 parts by weight of the anhydrosugar alcohol composition; The anhydrosugar alcohol composition comprises: a) monoanhydrosugar alcohol; b) dianhydrosugar alcohol; c) a polysaccharide alcohol represented by the following formula (1): d) anhydrosugar alcohol derived from a polysaccharide alcohol represented by the following formula (1); and e) one or more polymers of a) to d); A method for producing a polyol composition comprising: [C4] (In the formula, n is an integer from 0 to 4.)

8. The method for producing a polyol composition according to claim 7 further comprises the steps of hydrogenating a glucose-containing saccharide composition to produce a hydrogenated sugar composition, heating the resulting hydrogenated sugar composition in the presence of an acid catalyst to cause a dehydration reaction, and subjecting the resulting dehydration reaction product to thin-film distillation to produce an anhydrous sugar alcohol composition.

9. A method for producing a polyol composition described in claim 8, wherein the glucose-containing saccharide composition contains 41% by weight to 99.5% by weight of glucose relative to the total weight of the glucose-containing saccharide composition.

10. The hydrogenation reaction is carried out under a hydrogen pressure condition of 30 to 80 atmospheres and a heating condition of 110 to 135°C, The dehydration reaction is carried out under reduced pressure conditions of 1 mmHg to 100 mmHg and heating conditions of 105°C to 200°C, The method for producing a polyol composition according to claim 8, wherein the thin-film distillation is carried out under reduced pressure conditions of 2 mbar or less and heating conditions of 150°C to 175°C.

11. A polyurethane prepolymer prepared from the reaction of the polyol composition of any one of claims 1 to 6 with a polyisocyanate.

12. A chain extended polyurethane produced by reacting the polyurethane prepolymer of claim 11 with a chain extender.

13. 13. The chain extended polyurethane of claim 12, wherein the chain extender is selected from the group consisting of 1,4-butanediol, isosorbide, hydrazine monohydrate, ethylenediamine, dimethylhydrazine, 1,6-hexamethylenebishydrazine, hexamethylenediamine, isophoronediamine, diaminophenylmethane, or combinations thereof.

14. (1) reacting the polyol composition according to any one of claims 1 to 6 with a polyisocyanate to produce a polyurethane prepolymer; and (2) reacting the polyurethane prepolymer with a chain extender; A method for producing a chain extended polyurethane comprising the steps of:

15. A hot melt adhesive comprising the chain extended polyurethane of claim 12.

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